Pi1; fa /-152
EPA/600/2-87/013
January 1987
STACK TESTING OF T.:IF. MOBILE PLASMA ARC UNIT
by
Mark Gollands, Edward Peduto, Joanna Hall, and Howard Schiff
Alliance Technologies Corporation
(Formerly GCA Technology Division, Inc.)
213 Burlington Road
Bedford, MA 01730
EPA Contract 68-03-3243
EPA Project Officer
C. C. Lee
HAZARDOUS WASTE ENGINEERING RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OH 45268
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V ntPO1*"' ND
LPA/600/2-87/013
TECHNICAL REPORT DATA
(Ptietr rttd liutrvetieiu OK IA» «rtrv I
TF
'TfSfy'TsTffsotes
1 TITLt ANDSJ5TITLI
iroat DATI
Januarv 1987
Stack Testing of the Mobile Plasma Arc Unit
COOL
i AUTHOWSI :iark Collands
Howard Schiff
Edward Pcduto
Joanna Hall
Alliance Technologies Corporation
(Formerly CCA Technology Division, Inc.)
213 Burlington Road
Bedford, MA 01730
It CONTWACT/&RAfcT NO
68-03-3243
12 CrONSOHIMG AGtMCV MAMC AND ADDMICS
HAZARDOUS WASTE ENGINEERING RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI. Oil 45268
11 """I O» Ml'DfT AND rtnica CCvlHtS
CODE
EPA/600/12
IS
16
A trial burn program involving a plasma pyrolysis system was conducted at the
Royal Military College, Kingston, Ontario. The plasma pyrolysis unit was
developed by Pyrolysia Systems, Inc. under contract to the New York State
Department of Environmental Conservation (NYSDEC). HWERL-Ci under a joint
agreement funded the performance evaluation phase*
Trial burns were conducted while firing carbon tetrachloride and poly-
chlorinated biphenyls which are RCRA and TSCA regulated compounds respec-
tively. Results from the trial burns indicate that the system is acceptable
for treating these two compound classes in reference to the RC.ii (> Sy.99Z DRF.5
and TSCA (> 99.9999Z DRE) requirements.
(CtT WORDS AMD DOCUMINT ANALYSIS
I PI KTIf IIWS'OPtN IWDtD TtMMS
r COi*T' Field Clour
B blSTMlBLmONSTATCWCMT
RELEASE TO PUBLIC
I PA r cm 2230.1 (Bev. 4.77) PBIVIOUI BDITIOH K OD»OkBTi
ie ClCUOlTT CLASS
UNCLASSIFIED
Jl MO O> "CIS
*
.TO SICuaiTY
UNCLASSIFIED
27
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NOTICE
This Final Report was furnished to the Environmental Protection Agency by
the Alliance Technologies Corporation (formerly GCA Technology Division,
Inc.), Hertford, Massachusetts 01730, in fulfillment of Contract No.
68-03-3243, Work Assignment No. 6. The opinions, findings, and conclusions
expressed are those of the authors and not necessarily cl.ose of the
Enviromnent.il Protection Agency or Che cooperatinR agencies. Mention of
company or product names is not to be considered as an endorsement by the
Environmental Protection Agency.
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FOREWORD
The Environmental Protection Agency'was created because of increasing
public and governmental concern about the dangers of pollution to the health
and welfan; of the American people. Noxious air, foul water, and spoiled lan.l
are tragic testimony to the deterioration of our natural environment. The
complexity of the environment and the interplay between its components require
a concentrated and integrated attack on the nroblems.
Research and development is the first necessary step in problem solution;
it involves defining the problem, measuring its impact, and searching for
solutions. The Hazardous Waste Engineering Research Laboratory develops new
and inproved technology and systems to pr-vent, treat, and manage hazardous
vaste pollutant discharges. This publication is one of the products of tha;
research.
This document presents info-mation which can be used to assess the
feasibility of destroying hazardous .raste using a mobile plasma pyrolysis
unit. Trial burns involving KCKA and TSCA regulated compounds we.-e conducted
during which time all environmental release points were sampled and actual
release rates quantified.
Thop.:a3 X. ilauscr, Director
Hazardous Waste Engineering
Regional Laboratory
ill
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ABSTRACT
The mobile plasma arc system developed by Pyrolysis Sysrems, incorporated
(PSI) underwent an extensive frial burn program in Kingston, Ontario, Canuia.
The- objectives of this program wen*, to evaluate the performance of the system
and to establish its destruction and removal efficiency (Wi) capabilities
while pyrolyzing both RCRA and TSCA regulated hazardous waste feeds. The
emissions were sampled and analyzed for: carbon tcCrachlori.de VCCl/.),
hydrogen chloride (HC1), polychlorinated biphenyls (PCfls), polychlonnated
dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF), and
particulate matter. Of notable concern were polynuclear aromatics (PNAs)
contained in the scrubber water discharge. Samples of the scrubber water
generated during the system operations were also analyzed for CC1* HC1
PCBs., and PCi)D/PCDF.
During the CCl^ trial burns, the pyrolysis system met the established
RCRA requirement with a nRF. of CCl^ of greater than 99.99 percent. The
CCl^ emissions averaged 24.98 x 10~6 kg/hr with an average input of
63.0 kg CCl^/hr. HC1 emissions averaged 0.25 kg/hr. NOX and CO emissions
were C.35 and-0.14 kg/hr, respectively. CCl^ discharged through the
scrubber water averaged only 6.21 x 10"^ kp/hr.
Results of the PCB trial burns indicate that the pyrolysis system
destroyed the PCBs at a level of greater than or equal to 99.9999 percent
ORE. PCB stack emissions during the three tesf runs ranged from Not Detected
(ND) to 0.11 x 10~6 kg/hr with a system ORE of greater than 99.9999
perccnL. PCDD and I'CDl emissions were in ranges of NU to U.U2B x 10~° kg/hr
(PCDD) and 0.082 x 10~6 to 0.304 x 1Q-& kg/hr (PCOF). HCl and particuljte
matter emissions averaged 0.0039 and 0.028 kg/hr, respectively. NOX and CO
emissions averaged 0.47o and 0.053 kg/hr, respectively. PCDUs were not
detected in the scrubber wjter discharge. PCUFs wo; e detected ir. very small
concentrations in only the first test run. I'cjBs flucli.iiKed in tni scrubber
water ranged from NB to 93.1 x 10~° kg/hr. PHA conc.unt.atLons in the ppb
range were detected in both thu spent scrubber water and the stac.k gas.
IV
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CONTENTS
Notice
Foreword
Abstract lv
ViRures vi£
Tables viu.
I. Introduction I
2. Summary, Discussion of Results, and Conclusions j
Project Summary 3
Carbon Tetrachlonde Trial Burn (,
PCB Trial Burn \\
Conclusions ^y
3. Facility Description jig
Process Description 30
4. Sampling locations -$4
Waste Feed j/t
Reactor Ash 34
Scrubber Water 34
Host flare Product Gas 34
Preflare Product Gas 37
5. Sampling Procedures 41
Waste i'ced 4^
Reactor Hearth Ash 41
Scrubber Water 42
Postflare Stack Gas 42
6. Analytical Methods 37
Waste Feed and Scrubber W.-jter 57
Postflare Stack Pas .• 58
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CONfENTS (continued)
7. Quality Assurance/Quality Control ....
Introduction j 6l
Project Description .........'.'.' [ °l
Project Organization and Responsibilities ! °!
Precision, Accuracy, Completeness, Representativeness ' '
and Comparability
Sampling Procedures .' b2
Sample Custody '.'.'. by
Calibration Procedures and Frequency." . ,!
Analytical Procedures l
')ata Reduction, Validation and Importing.' ." " ' ly
Internal Quality Control Checks „
Performance ana System Audits ..-...'." .
Preventive Maintenance ... 2
Assessment of Precision, Accuracy, "and'compU^ness .' .' .' ?2
Corrective Action .
73
References
74
VI
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FIGURES
Number
Page
3-1 Facility area top view 31
3-2 Process schematic ot the PSI plasma pyrolysis unit S'i
4-1 Plasma pyrolysis system flow diagram J5
4-2 Wnste feed sampling location jt>
4r3 Post flare emission sampling locations JB
It-It Sampling point locations jy
5-1 Continuous monitoring sampling schematic 44
5-2 Volatile organic sampling train schematic 4e
5-3 Integrated gas sampling tiain 50
5-4 Modified Method 5 train 52
5-5 Modified Method 5 sa:nnle point locations 53
5-6 Gaseous HCl sampling train 55
6-1 Modified Method 5 tr^in O'^anic analysis flow scheme 59
VII
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TABLES
Page
2-1 StoRe II, Test Series 1 Sampling Parameters 4
2-2 Stap,e III, Test Series 3 Sampling Parameters 5
2-3 CCl/, Test Burn Schedule 7
2-4 StaRe II CCl,t and HCl Emissions 8
2-5 Combustion Parameters - CC'/, Trial Burns 9
2-6 PCB Test Burn Schedule 12
2-7 Waste Feed Composition and Keed Rate 14
2-8 Scrubber Water - Volatile Mass emission Rates 15
2-9 Scrubber Water - Senivolatile Mass Emission Kates lo
2-10 Scrubber Water - Chlorinated Species Mass Emission Kates .... 19
2-11 Postflare Stack Gas Combustion Data - PCB Trial Burns *0
2-12 Postflare Stack (Jas Particulatc and HCl Emissions Data 22
2-13 Postflare Stack f;as - Scmivolatile Mass limis&icn Rates /J
2-14 Postflare Stack Gas - Chlorinated Semivolatile Orpsnic Compound
Mass emission Rate 24
2-15 Plasma Pyrolysis System DKE Cor PCBs in a Liquid Waste Keed ... ^8
5-1 Preflare and Postflare Emission Parameters. Measurements 43
5-2 CEM SamplinR Parameters and Methodology 45
7-1 Summary of CCH Precision, Accuracy, and Completeness i>J
7-2 Analysis of a Laboratory Control Sample for Chlorides b4
Vlll
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TABLES (continued)
Number
7-3 Analysis of a Matrix Spike Into Scrubber Water for Volatile
Organics ..........
Analysis of a Surrogate Spike Into Scrubher Water for
Volatile Organics .........
7-5 Analysis of Senivolatile Organic Macrix Spiked Compounds
(Percent Recoveries) .....
7-6 Analysis of Semivolatile Organic Surrogate Spiked Compounds
in Sample Aliquots ......
••••••
7-7 Particulatc Matter emissions Correction
i x
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SECTION I
INTRODUCTION
The U.S. Environmental Protection Agency's ilazardous Waste Lngineenng
Research Labc-ratory (I1UKKL), Cincinnati, Ohio, and Che New York Slate
Department of Environmental Conservation (I.'YSDEC) establishes a Cooperative
Agreement in 1981. The Coopcr.-.l we Agreement called for the con-it ruction aiio
ttstins of a mobile pilot-scale plasma arc system for the high efficiency
destrjcrion of hazardous waste. The capacity of the system is nominally
designed to be four kilograms (ft. 8 pounds) per minute, and to 'it, with
ancillary equi^ient, in a 45 foot trailer. The concept of the plasma arc is
th.T it uses very hir.h intensity energy with temperatures approaching IU,0'JO°C
to break bonds of hazardous waste chemical molecules down to the atomic
state. The re comb in.it 10:1 of those atoms results in molecules such as
hydrogen, carbon monoxide, carbon dioxide and hydrochloric acid. The
off-R.ises from the plasma svstcia are subsequently scrubbed to remove
hydrochloric acid and flared to renove combustibles.
In Qener.il, the appiojch taken for chis l-.PA/NYSUEC Cooperative A^roencnt
involves fo ir phases of activity. Implementation of each phase was subject ..o
the i:PA/NYS9CC approval of the preceding phase results. 'Hie lirat two pn.'sps
were pcrforiued in Canada with the cooperation ol Canadian Federal, Provir.ci.it
and loc-il an t hnrit ies; tl's-third and fourth nii.ises wi'i In.- perfor>-.CQ 1:1 tiic
State of New York. The total Cooperative Hrjgraia is configured as follows:
Phase I: Construction and shakedown of the mobile pla^.T.j arc system
by the vendor, Pyrolysis Sybten,s, inc.
I'hase II: Performance testing of the plasma system .it fu* Kingston,
Ontario test site (OCA involvement).
Phase III: Transportation, installation and verification ot system
performance at a site- in New York .SUitc.
Pnase IV: Demonstration tests as dusign.-ited by i-nttDLC tor permitting
purposes Jt a New Yjrk State hazardous waste
The vendor, Pyrolysis Systems, inc., completed t'.vz construction .inn
shakedown phase (Phase I) at the Kingston, Ontario tesi site by
December 1934. The unit was then su:taolc lor the initiation of :l-e Pnase II
performance tests.
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GCA's involvement began with Use initiation of Pliase II sampling
activities in February 1985. So«/er?l postponements occuircd prior to this
time which furthe- delayed pro-iaratory activities and eventual Mobilization of
the test crew and equinmer.t. .i'lOoili^dtion and- the initiation ot Phase H
activities were Eina.l- accomplished in February 19S5.
Phase II consisted of several stages of perforraanre testing. St.i/x I
included equipment operation and shakedown w'lich was performed by PS I prior to
GCA's arrival onsite. Stage II and Stage III were furtJer broken down into
several Lest series which were dr5si)»n
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SECTION 2
SUMMARY, DISCUSSION OF RESULTS, AND CONCLUSIONS
PROJECT SUMMARY
The measurement activities were conducted in accordance with the Duality
Assurance Project Plan (QAPP, Reference I) which was prepared and submitted
under EPA Contract No. 68-02-3698, Task No. Oil. Any deviations from this
QAPP have been addressed iti Section 7 of this report.
The primary purpose of Stage II was to demonstrate destruction
capabilities of waste materials containing regulated chain chlor-nated
ecru pounds. One test series was conducted and involved three 60 minute tests.
The only waste feed component was CCl^ contdined in an MEK, methane* I , and
water blend. The primary pui.-po.sfi was to demonstrate proper uCl removal
through the scrubber process *nd the destruction of one of the harder to
destroy confounds
The St.iRe II sampling and analytical parameters are shown in Table 2-1.
The various samples were collected and analyzed onsitc. Spent scrubber wster
was stored in one cobic meter tanks pending completion of the onsite analyses
and a demonstration of compliance with the Ontario Ministry of the Liivironmcnt
(HOE) effluent guidelines.
The primary purpose of Slatja III was to demonstrate the destruction
capabilities of the system using a waste feed containing more complex
chlorinated aromatic compounds, namely Askarel. The Askarel was comprised of
a mixture of three Aroclors and trichlorobenzene with the balance of the waste
feed being MEK and mcthanol.
Stage III Test Series 2 consisted of three 60 minute test burns which
were monitored by 1MET. Testing was initiated in December 1985 and was
completed bv Febru irv 1986. As GCA had no involvement in these I hour I'CB
burns, no data Lrom those burns are presented in tnis report. bCA Wus
mobilized and onsite again in. February 1986 to begin Stnge III Test Series 3
which consisted of three 6-hour enduispre test burns. Due to the possibility
of system malfunctions and lengthy delays, the sampling period ujs shortens*
to 4 hours. Testing commenced on February 12 and cr.dcd hetuuary 2.2. l^bu.
the first test lasted 115 minutes (l hr 55 min) before shutting down due to a
toich power malfunction. The second test on February 20 lasted for the tull
4 hours, as did the third and final burn on February 22. The parameters
measured during Stage III Test Series 3 are shown in Table 2-2.
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TABLE 2-1. STAGE II, TEST SERIES 1 SAMPLING PARAMETERS
Sampling point
Measurement parameter
Post flare product gas
Spent scrubber water
Waste feed
Reactor ash
02, CO, C02, HCl, NOX, CC14,
flue gas velocity and temperature
CC14
Sample and archive
Sample if available and archive
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TABLE 2-2. STAGE III, TEST SERIES 3 SAMPLING PARAMETERS
Sampling point Measurement parameters*
Postflare product flas 02, C02, CO, NOX
HC1, particulate matter
samivolatiles, VOCs, PCUDs/PCDFs,
PCBs, TCBs
flue gas velocity, temperature,
moisture
Spent scrubber water serai-VOCs, VOCs, TCBs, PCBs,
PCDDs/PCDFs
(Reactor ash) if available
Waste feed PCDDs/PCDFs, PCBs, TCBs
*VOCs = volatile organic compounds
PCDDs = poIyen lorinated dibenzo-p-dioxins
PCDFs = polychlorinated dibenzofurans
PCBs = polychlorinated bipheny'.';
TCBs = total chlorinated benzenes
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™e data, are reported in essentially two parts. The first represents
data obtained during StaRe II, Test Series I during which time carbon
fpnH'l TKde WSS the Selected Principal organic hazardous constituent
IPOHU. These data include scrubber waste feed, water, and stack gas
parameters obtained during the testing. The second data group represents
information obtained under Stage III lest Series 3 during which an Askarel
waste blend was the selected waste feed.
CARBON TETRACHLORIUK TRIAL BURN
Sampling for CC14 emissions was conducted during Stage II Test
?n»^' \ '? determine the Derail CC14 destruction and removal'efficiency
(ORE) of the system. CC14 was selected as the principal organic hazardous
constituent (POHC) because its very low heat of combustion suggests it is a
difficult material to be thermally destroyed, based on EPA's current ranking
guidance (Reference 2); it is readily available, and it is relatively
inexpensive. Consequently, trial burns are frequently conducted using CCU
as the POHC. icsting was initiated on February 16, 1985, after 4 days of
plasma arc system preparation and test equipment set up. The test schedule
was as shown in Tahle 2-3. The results from the three completed 60 minute
test runs are shown in Tables 2-4 and 2-5.
During the three tests, waste feed rates of 2.82, 2.26 and 2.83 liters
per minute, respectively, were introduced to the system. This corresponds to
mass feed rates nf (,4.2, 60.6, .ind 64.2 kilograms CCU per hour (kg/hi-;
respectively Scrubber water flow ,-.« during these tests were, respectively
33, 30, and 32 liters per minute (L ,„.-,). Stack gas flow rates during these
tests were 38.13, 29.69, and 29,61 tfr> standard cubic meters per minute
\tn /mm).
Waste Feed - CClA/MfcK/MEOH
The waste feed blend of CC14 and methyl ethyl ketone was introduced at
rates averaSin^ 2.82, 2.26, and 2.83 L/min. These correspond to CCU mass
feed rates of 64.2, 60.6, and 04.2 Lg/hr. These figures were used in
calculating the destruction and renoval efficiency (DKK) of the syste... shown
in Table 2—4.
Scrubber Water
Scrubber water samples were taken and analyzed for CC14 concentrdtions
which were then combined with scrubber water flow rates to yield CCU
discharged to the sewer. The concentrations of CCl, found in the scrubber
wat.*r were 1.27, 5.47, and 3.26 ppb (,jg/L), respectively, for the three 1-hour
tests. The mass discharge rates are presented in Table 2-4.
Post flare Brack Cas
During the CCU, vaste feeri burns, samples of the postflare stack gas
were obtained and analysed for 1ICI and CC14. In addition to these
parameters, the stack P,as flow rate, temperature, and bulk gas constituents
VU2» C0. C02 and N(V were monitored on a continuous basis.
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TABLE 2-3. CCl4 TEST BURN SCHEDULE
Bate (1985)
Occurrence
Test Duration (min) CormnenCs
2/16
2/18
2/23
2/24
2/26
2/26
1st burn
2nd burn
3rd burn
4th burn
5th burn
6th burn
15
60
26
38
60
60
System malfunction
1st complete test run
System malfunction
System malfunction
2nd complete test run
3rd complete test run
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TABLE 2-4. STAGE II CC14 AND HC1 EMISSIONS
Ddte, 1985
Test duration, -iin.
Waste FyeJ Pararicrcrs
Wa-.tu Feed Composition
CC1(,, mass "
MEK/MeOH
Specific gravity
kg/L
'«a!>te Feed Flow Rate,
L/min
kg/Kin
CC14 Feed Rate, kg/rim
kg/hr
Scrubber Water Parameters
Disc large Flow Rate,
L/nin
CCl^ Conccntrnt ion,
ppb (ug'k}
CClf, Discnarge Rate,
kg/hr
Ib/hr
StacV. Gas Parameters
Average Flow Rate, ra3/mina
Average Terapeiature °C
•r
KCl Cone. , mg/m3a
I'Cl Emissions, kg/hr
Is/ar
CC14 Cone. , FPbC
CClfc Emissions, kg/hr
Ib/hr
Systcr. CCli DRE , 5
3 1
2/lS
60
35
45
1.08
2.82
3.05
1.07
64.2
33
1.27
2. 51x10"'
38.13
90&
1,666
b
KM
29.27x10"*
599.99
Run 2
2/io
60
4C
60
1.12
2.26
2.53
1.01
60.6
30
3.47
O.SSxlO"6,
21.71x10"°
29.69
1.048.3
821
1,510
138
0.25
0.55
22.79xlO"6
50.14x10""
>99.9V
Kni 3
2/2b
60
35
65
1.06
2. SI
3.06
1.07
64.2
32
3.26
?;:££-*
29.31
1,052.7
•o92
247
0.^***
0.97
22.59x10"^
50.36x10 6
>99.99
Av . •-.•?-
60
36
64
1.09
2.64
2.83
1.05
63.9
32
3.33
6. 21x10"*
32.5-'.
1,1-9.1
807
l,4Si
193
0.35
0.76
24.96xlO"6
54.96xlO"6
^99.99
a!jrv standard condifions as defined by 20'C ?nd 760 tar. Hg.
bHCl sampling conducteo at oreflare loca:ion. SampliRg suspended due to
carbon plugging of train
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TABLE 2-5. COI1BUSTION PAKAKKT&KS - CC14 "UIAL BURNS
Tea t run
Date, 1985
Stack Cas in-Vain3
I* Iowa i- rite ft"/mina
Stack Gas Temperature, "C
°F
NOX Concentration, pptn (v/v)
Emission Rate, kc/hr
Ib/hr
CO Concentration, ppri (v/v)
Emission Rate, IiR/hr
Ib/lir
02, percent
C02i percent
I
2/18
38.13
1,346.3
908
1,666
106
0.46
1.02
W
0.13
U.28
12.7
6.0
2
2/26
29.69
1,048.2
821
1,510
92
0.3:
0.69
57
C.12
0.26
14.4
b.7
3
2/26
,19.81
1,05?. 7
692
1,277
tJl
0.28
0.62
81
0.17
0.37
15.1
4.9
Average
J2.54
I, l<*9. 1
807
1,484
93
0.35
0.78
62
0.14
O.Ju
14.1
b.5
aDry standard conditions as defined by 20°C an
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KCI--
During Run I, hydrogen chloride was sampled at the preflare location (see
Figure 5-6) but was aborted after 20 minutes due to plugging ot the sample
line by the hifih carbon and moisture content of the gas stream. This sample
was invalidated. No further testing was attempted at this location after
several flarebacks occurred, causing safety concerns at this sampling
location. The sample train utilized in obtaining the IICl samples is described
in Section 4.0. The concentrations of HCl found in the stack gas were 1J7.7
and 247.2 mg/m3 for Kuns 2 and 1, respectively. The results of the IICl
testing are further summarized in Table 2-4.
Carbon Tetrachloride--
CCl^ samples were obtained from the stack gas using an integrated bag
sampling technique whereby a volume of stack gas was drawn into a "tdlar bay
at a constant rate over a period ot" time The gaseous samples were cnen
subjected to onsite analyses by gas chromatography equipped with an electron
capture detector (GC/ECD). The concentrations of CC14 present in the stack
gas during Runs I, 2 ani 3 were all telow the detection limit of tne
analytical instrument (less than 2 ppb). For the purposes of this report, and
the establisnment of a reportable ORE for the system while fired witli a
CCl^-congaining waste feed, CCl^ emission rates of 29.27 x 10~",
22.79 x 10~6, and 24.93 x 10"6 kg/hr were used in the calculations. The
ORE is calculated using only the stack yas a-iission rate ar.* does not include
CCl4 discharged in the scrubber water. Therefore, the established URE's for
Rurs I, 2, nnd 3 are all greater than 99.99 percent. Table 2-4 contains a
suirrrary of the stack gas data including the system's IJKIi.
Oz, C02, CO and NOX—
In addition to IICl and CCl^ sampling and analysis, combustion
parimeters were measured in the postflare stack gas via fiCA's continuous
emission monitor system (CEMS). Samples were extracted on a continuous basis
l-v means of an in-stack probe, filter, nnd heated sample line and passed
r.irough a gas conditioning system and valving system to the calibrated
analyzers. The gas streams were analyzed tor 02, CO^, CO, and Nu_,
c jnc--ntration-,. Resultant d.ita (millivolt output) wore input directly to tne
Fluke Data Acquisition System and strip chart recorder. The Fluke output was
f'lr.natted into test: report form and yielded results in ppn, percent, and
r-junds per hour, as necessary. In addition, stack gas velocity was recorded
contiruously via a pitot tube/pressure transducer hookup to the Fluke computer
system. Temperature was monitored similarly using a thermocouple/Fluke
hookup. All Lest combustion data are suu.nanzed in Table 2-5.
As is the: case with most combustion sources, NOX and CO are good
indicators of combustion temperatures and efficiency. During startup and
shutdown operations, the flare is quite unstable due to the nonsceady reactor
project &as supply. This is due largely to the fact that, during startup, the
re.'ictor requires a minimum time period to reach equilibrium temperature.
Because of the instability upon startup, the system was brought up to
oucrating temperatures on a waste feed containing iionchlorinated compounds,
such as methyl ethyl ketone (MhK).
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in the system us the new waste entered the plasma as may be evidenced by
changes in the postflare stack gas temperatures and concentrations ot Oy,
C02> and NOX. GeneraIly, once system temperatures stabilised, CO
concentrations were relatively constant at levels of less than U.17 kg/hr.
Different types of waste, and even the same waste wil'i slightly varying
compositions, seemed to affect varying system responses. As such, although
the system could be controlled to operate within a certain range, the
repeatability of tests using different waste feeds remains a question. This
is due, in part, to the chlorine composition, density, and solids content
found in different types of liquid waste feeds.
PCB TRIAL BURN
GCA's involvement during Stage III began with Test Series 3 wherein
sampling took place during tha conduct of three endurance PCB trial burns.
The waste feed during these burns wis comprised of a blend of three Aroclors,
trichloroben/.ere, methyl ethyl kef one, and mechanol. Askarel
(Aroclo-/Lrvchlorobenzene blend) comprised approxinately 25 percent of ihe
waste fiicd by weight. Test Series 3 was included in the program to test the
plasma pvrolysis system over a period of 4 hour-, while a waste of this type
was introduced. Originally, three 6-hour runs were slated for this test
series. However, the target run times were reduced to four hours in a joint
decision by PSI and NYSDEC personnel in an efforc to conserve waste feed and
to complete the sample runs in a timely manner. Ihis shortened run time was
also deemed sufficient for allowing adequate detection limits for cne required
analytical parameters.
During the firs: trial burn (CCA Rjn 3-1, February 12, 1986), sampling
endfid after 115 minuter. (I hr 55 mm.) due i.o torch power problems within tne
pyrolysis system. The second and tnird burns (CCA Runs 3-2 and 3-J,
February 20 and 22, 1986, respectively) wcte each completed atter ^.U minutes
(4 hours) of satrple time. During ,{un 3-2, sampling was interrupted for
approximately 30 minutes due to an offsite power grid loss causing a s>ysteni
upset. The syste-a was brough* bacl. on line with the MbK/KEOli waste feed and
sampling was resumed 10 minutes after the switch baok to the PCb waste teed
blend was made. During all operation of the pyrolysis system, no PCB
containing waste was introduced prior lo the system first being stabilized on
the MEK/MEOH feed. Additionally, r.o sampling was conducted while tne system
was solely on the MEK/MEOH feed, in transition to the PCb waste feed, nor
during a svsttm upset period. The test schedule for Stage III Test Series J
was an shown in Table 2-6. The resultant data from these test runs are
presented in this section.
During the three Lest runs, the PCB waste blen.1 was introduced to the
system at rates of 2.10, 2.33, and 2.20 kilograms per minute (kg/mm),
respectively. The average PCI5 content of this feed (total, mono through
i1ecs..hlorinated biphenyls) was 12.6 percent by weight. The total nass lJCli
input was 0.26, 0.29, and 0.28 k«/min., respectively, tor the three runs.
Scrubber water flow r,.tes averaged 30.5, 33.0, and 12.5 liter:, per minute
(L/min). Stack gas flow rates w°re 45.43, 36.41, and 35.81 dry standard cubic
meters per minute (m-Vr.iinJ, for Kuns 3-1, .'!-?, and 3-3, respectively.
U
-------
Date
1ABLL 2-t.. !JLii TEST BURN SCHEDULE
Occurrence
"ijbi duration (mm)
Comments
2/12/85
2/20/86
2/22/86
I si burn
2nd liurn
3id burn
Hun 3-1 abbreviated
•Juu to system iiial-
tuncrion.
Run J-2 inrerrupLed
for about 1'2 hr-
ccinpletcd
Run J-J, slight fan
problems during
pore change bin no
interrupt on-
completed .
\i
-------
rt Fc.nl - Askarel/Mr.K'/Mi:Oli
The i'CB wasEO f.jed blend was introduced at .-in average rale of i.l\ ki'/niiu
with a I'Cli mass irar.it of 0.2ft l-r./inin or ll>./ k?;/hr. 'iliis mas.s input includes
mono tlirouj'h ilecachlnrin.-ited bip'nenvls. Interlaced samples vcii> obt.-.ined
during each test run from the valving assembly JUSL prior LO the tec.il ring ot
the reactor vessel. AC this point, the waste feed ulund was well mixed and
representative of that ted into tlid plasma reactor. The samples -.-ere ana l> zed
for ic-Ml PCli-i, chloroocnzenes, polychlorina trd dibenzo-p-d loxins (t'CDDs), and
polych lor mated c" jbcnaofurans (I'CUi-'sJ. Data jn waste U-aJ compos it ion and
feed rate are presented in Table 2-7.
S*- rubber JJa^.ur
Scruiibcr water samples were collected tl.iri.nR uach LCSL run and analysed
for volatile and sooivolatiie compoiinds including 1'CBs aim I'CUUj/l'ClJl's.
Durini; Runs 3-1, 3-2, and 3-3, scrubber water flow rate was J6.5, J3.U, and
32.5 L/min, respectively. The scrubber wati-r samples were .inalyzua by
laboralon* and the resultant data are summarized in the following
Volatiles —
The vo'alile compounds found in the scrubber water were principally
benzene, toluene, chloroben-senc, and sLyrene. Tueir mj!.s emission ran-b,
based on tlieir aqueous concentrations (iWL) and the scrubber discharge rate
are shewn in Table 2-8. In addition to those compounds listed above, rwo
others were detected albeit at concentrations i>cneaih Lhe detection limit of
the instrunont. flicse were tr.ms I, J-d ic'ilorocciiene in Kun J-2 .ind chlorororra
in Kun 1-3. Chloronth.inp and 2-butanone wore- also found in Kun 3-3 in
measurable quantities. The scrubber water sample from Kun J-l vat, lost ciue, lo
K ing and breakage of the V(JA vials.
Semivolat i los--
Semivolat ilc components of the scrubber water discharge wore sampled liv
nwans of compositing samples in a large; container during th*> course 01 u.ch
test riiii. Samples were s^lit in order that a larKC aliiuoC could be sent to
Zcnon Knvirnn.nent.il, Inc. to conduct Lliju 1'i.ii, cli loroben;:enf , and I'CUu/l'uUr
an.Tlvses. 'Hiesn data are presented .ind discussed separately. Tne remain mi;
aliquots were transnorted to (JOi's laboratory to .conduct inrther bC-r.iivolat lie
an.ilv-.es. Gnacrally, Lhe com.wnnds detected and quant ilied are si.stfr
connpoiinds to naphthalene and nyrenc. They are presentud in Tan ie 2-y witu
tlmir associated concentrations and mass discharge r.-ites. 'Ihe concentrdt'onb
presented in tins ublo are combined aqueous and carbon analy<.f.l inatriceb, as
the sample were two-ph.i«ed. r^nerally, the carbon lavcr had hif.ln.-r
concep.t rat ions of sn.nivolat i le compounds than tliliarated fron- the. aqueous solution, fonnin;; a Lop L.iyer
with a lii^ht, nerin»ue-type consistency. In oilier samples, the carunn
remain?'! in suspcns inn or nraduillv settled out over a period of time. inis
incoucisfencv in carbon l.i;>ur Conmtion n.-iy be d»i<: to varyinh LO.IS iscc'nc> u:
the scrubber water in which the density of the carbon is R re a tar than that ol
the aqueous boluLion phase. Additional an.ilytical data are presenCcd in
siil)scrinunt sections.
13
-------
TAB!.!: 2-7. WASTU FLCD COMPOjITIUN Ai.l) FEI.l) KATb
Date
2/12/86
2/20/f.O
2/22/86
Run No .
J-l
3-2
3-3
PCU content3
percent
U.3b
12. y1
12. 8b
•taste feoil
flow r.ite (kg/ii-iu)
1. 10
2.33
2.20
I'CII mass
input (kg/nnnj
U. JO
I,. 2 9
• 0.28
"""Total PCBs (mono-dec.ichlorinat.ed biplicnyls).
"From tenon's analyses.
-------
TABLE 2-8. SCRUBBER WATER - VOLATILE ".ARS EMISSION RATES
«S.I. — ~~ —~— ™ Bt.m.~~
Rate Kiin f'
2/20/B& :-:>
2/2?/86 3-3
Coripound
1 12-di.<.-lll.crl>et•llf>.nt_•
^Jen;'.^>nu
Toluene
Chlorobcnzcno
Styrenc
Chloroctha.io
Chloroform
Hcnzonc
Tnluone
Chlorobunzene
2-biitanonc
Styronc
Cone en-
tree ion
Sa/D
2a
8/<0
41
S3
86
23
33
770
29
50
12
68
Scrubbor Compound rwss
wAtcr flow u.niss'.on rate
rale U/min) UO"6 kg/hr)
33.0 't
1,063
'",
16A
17C
32.5 /.5
6
1,502
57
98
?3
i3J
it present benr.-illi clcLecLion liinits. Kcsul.i should b
scir.iqiinnr. if .-Li vc .
-------
TAB-E 2-9. SCKL'BBER WAVER - SUMIVOLATII.E MASS EMISSION
Datfi Run I-
2/12/86 3-1
?/22'86 3-2
-sr-» 1 -i. — T» * - j ^**— i-a-
Com pound
Napthalf»ne
AccnaphthalfMiu
AcenAphchenA
Kluorone
ijhenanthreni
Anthracene
Fluoranthene
pyrene
Benzo (A) Arithracene
Chrysene
IJenzo (B) Fluoranthene
Benzc (it) Flucranthene
Bonzo (A) V*yi.enc
Indeno(l2J-CU) fyrene
Ben
-------
TABLE 2-!> (continued)
Date Run # Compound
2/22/36 3-3 Naphthalene
Acenaplithalcne
Aeenaphthene
F lucre ne
Phenanchrene
Anthracene
FlucranUien
Benzo(K)Fluornnt:henp.
Benzo( A)Py rene
Indcno(l2J-CD) l^rene
Ben7o(t;Hi;Perylene
2-met!\yln.ipliChalene
Conccu-
tvation
(I..R/L)
8.90U
39.UOU
69
«1U
17,000
730
12.UOO
12.00J
690
850
960
A40
1,800
1.7UO
5,400
100
Scrubber
water flow Cor , ound raass
rate emission ratp
(L/mtn)a (L0~° fcg/lir)
32.5 l7,Jj>
7o,03U
LJ3
l,i&0
JJ.150
1,424
2J,^OU
2J,4JO
I.J40
l.biti
1,872
biti
3.51J
J, Jl")
1U, iJvJ
:y;>
aSc rubber wni.er flour/ire obtained £roia PSJ via NYSDf.C.
17
-------
PCBs, Chlorobcnze"."s, PCUDs/PCDFs—
Split scrubber water samples were analyzed by Zenon Uwironmental, Inc.
for PCB, HCDD, and I'CUF content. In .iddilion, Kun J-l scrubber V.JUT samples
vrire an.ilyzod for chlorohr.izenos, chlorophimols, ami benzo (a) pyrene. Tne
resultant data from tlic^e analyses are given in Table 2-10. Tne
concentrations £iven ire combined aqueous find cjrbon phase conceuLranorth of
each compound. As can be suen from tl.e data MI Table 2-10, I'llUus were not
detected in the scmbbci water in any of the runs. PCUFs, were detected in
only the first run .ind mono through decachlonnat ed biphenyls in Lhe lasr two
runs. It should be noted thac mono ar.d dichlorinated biphenyls represent.
approximately 89 and 81 percent of the total I'CU mass in Km:* J-2 ar.a j-j,
rcspcctivolv.
Pof.tClar.-i Stack Gas
Stack ,;.as sar.plcs were collected during each run utilizing a variety of
sampling ir.iins and methods to obtain the required parameters. The stack gas
constituents sampled for included 02, C02, CO, NOX, particulate matter,
HCl, volatiles, b-wivo latiles, PClls" and Pi.'UDs/PCi.'Fs. Also included were
measurements of p,as temperature, velocity, and moisture. As stated earlier.
Run 3-1 W-TS limited to 115 minutes of sampling Lime due to a malfunction of
the power supply to the torch. During the three Lest runs, some proolenis also
arose with the sampling equipment due to elm very cold weather causing saraole
lines and punps t.o freeze. Extremely tu^li temperatur-is witinn the stack
created numerous problems especially during Kun 3-2 \.hen };as temperatures
approached 1150°: (2lOO°r). KU-.IS 3-2 an.! 3-3 were sampled to completion,
however, tor total run times of 2-'»0 n>mutes (•+ hours) each. The Lest runs and
resultant nata tre suiumarizeil ami discussed in Llie followinj; subsections.
Combustion Data--
UuriiiR the three operational periods in which sampling runs J-l, J-2,
3-3 were conducted, tlie postflare stack };ar, wab uion.Lt.ored lor U t, t-U;, Co,
and NO,, usinj; CiJ'V's cor.tinuous emission mom Coring systen (L-LiSbJ. Tno^e
analyzers are Ircquently used in dcteniining combustion Plficiency for
diagnostic purposes as well .is for determining overall CO jnd/or ftO.x
emission races for rcgul.itory purposes. Th.-> cmissio.i rates are calculates
using stack sas How rates and the analy<:ei j,' .responses in concentration
(ppm-polliitaiit). The data are summari;. jd jud presented in Table 2-Ll in
conjunction with a'.ack gas flow rates ohtjincd during the semi volatile
sampling via MoJifiod Method 5 (MM5).
HCI--
i'missions of hvdrochloric -icid were sanplcd at Ihc poctflnrc stack to
determine stack «as concentrations as well ;ib the HCl uuss emission ratiis,.
Concentrations in tlie aai stiuara wort: quite low durinp. all tnree runs
.-'VCMr.ini: onlv 1.68 r^/ni-* for .in av/eugc on if si on late of O't. I inR/nun. or
0.0084 Ib/hr. The datd suiisnary is presen^eJ in Tjolc 2-12 with the
part icu Kite sniifsio
-------
TABLE 2-10. SCRUbDEK WATuR - CHUJRlNnTCD SPbUKS IIASS LMCSSION
DaLe Run if
2/12/86 J-l
Scrubber
Cone en- water tlov.
tration rato
Coinuniind
ill-Pen tachloroplienolb
Henso(A) pyrone
Tetra-Octachlorinated
dibenzo dioxius
Tctra-Octacls lor mated
dibenzo furans
Dichlorobenzene
Trichlorobenzcne
Mono-Dccachlorinaced
biplienyls
M)
329
t,"J
JO. 5
U.00072
0.2V
0.20
NU
a Analytical results from Xenon EnvironmenC.il, Inc.
b Scrubber water flow rate obc
-------
TABLC 2-11- POSTFLARi: ."LACK GAS COMBUSTION DATA - PCB TKl.'VL UUKNS
Par;ine
Dale
tUT
Test Duration, min.
Stack
Stack
Stack
Oiyaen
Carbon
Carbon
Oxides
Cas Temperature, °C
op-
Gas Velocity, in/sec
f t/inin
Gas Flow Rate, m^/'inn8
ft3/minj
, ixrccnt
Dioxi-le, percent
Monoxide, ppm
k;./hr
Ib/hr
of Nitrogen, ppm
kg/iir
Ib/hr
3-1
2/12/86
115
576
1,070
17.8
3,511
1,604.0
15.8
J.t
18
0.057
0.126
96
0.502
1.104
Run number
J-2
2/ -£0/80
240
'107
l,f}54
20.8
4,090
J6.MI
1,285.0
l,.0
5.1
20
O.U51
0.112
115
0.482
1.060
J-'J
2/22/86
240
8/1
1,599
19.5
3,843
J5.81
15. J
4.3
20
0.050
0.110
108
0.445
±ZL
765
1/44
19.4
3,814
i,JB4.7
15.0
4.4
\1J
0.05J
LM16
106
0.470
1.04ti
anrv st.-mrf.ird condition"; ilcfincrl .is 20"C and 760 i.m IV..
-dl)
-------
Part icu late Matter--
Prior to .TM.ilw.uv, the tlflS filro-s a:"! probe rinses for ?c;. ivo l=ti It
compounds, the participate caLch was weighed dnd ULGC! in calcul jn u»j>
particulate omissions from the stack. The results on the three test runs show
•in average; particnlatc concentration of 0.005 £rai.ub per J r y standard cuoic
foot (j>r/dscf) with an average omission rate of 463,2 m^/rain or U.061 Ib/iir.
Riiii 3-1 results were almost twice as l.igh ab thuse froip Kun 3-2 or j-j.
during run 3-1, the stack p.as temper.1. turn w.is much lower and the slack f;as
flow rate was higher than the two subsequent runs. The system problems winch
led to a siiorceninp, of the test period may also have caused the incnjaspr
grain lo.iriinp, (i.e., higher carbon concentrations in the reactor gas and
postdate stack i;aO. The data from the three test periods are compiled in
Table 2-12 alonR with IICl emission data.
Volatile Organic Compounds --
Thc post flare stack gas was sampled for volatile organic compounds (VOCs)
using a Volatile Organic Sampling Train (VUbTJ. The results of the bampling
are not available because the holding times of the samples and the uppei
temperature limits for stor.ige were exceeded. The results of tue analyses
would be deemed erroneous because it is unclear what the breakdown components
would be after the samples were allowed to becor.u wan.i. Extrapolating trum
the data obtained from the scrubber water analyses, the most prevalent
constituents in the preflare product gas coula be primarily benzene,
chlorobenzene, toluene (nctliylbenacne) and styrene (ccher.ylociizenej witn
boiling points ranging from 80 to 110' C. ft; is ebtiinarcjc en at m tnc
postflare stack %i*, only the h] Rlicr boiling conin»uri>is would he present
(i.e., si\rci"iivo la t lie Ornrfnic Compounf's--
Sanplinft for semivolat iln organ ics took place during each test period
nsino a Modified Method 5 (MM5) sampling train with an XAU surbcnt inoau le in
plo'-e. Coincident rfich this sampling IMS another similar train used for the
collection of semi jol^t lie organics solely tor analysis for I'Clis, PCUUs , and
FCDF&.
The semi vol a LI IP saiinlcs ".-ere ar..ilyze.t<5s are shown MI table 2-1 J. The sampling j.id analytical
iiiethods are ti-jsc.-ibed in Sections 5 am' 6, respect ivcl\ -
Chlorinated Species - I'CiJi,, fLD'Js, and PCDKs —
A sampling train similar to the one used for the collection ol
nonchloi inatC'd serii volat lie organic conpounJs, was used to Collect en loruiateu
samDles to hi analysed for polycnlorin.iLuil biphenyls (PClisJ, polyc n lorina ted
d ibnn;:ti-;>-(l ioxms (I'CUOs), .ind polyi.nlcrinaLod d iben^o Luran:; (HCUts^. luese
sample', were dnlivereil to ".en on Unvi rnnnicnLal, Inc. for bubsequunt nnalybis
follni/inK each test run. The re ult.--nt data from the three test rurio are
presented in fable 2-l-'>. A dostrucLion a.vl removal efficiency CiJKI.) tor tnc
21
-------
TABLE 2-12. PuSVf LAIE STACK GAS PART 1C I! LATE AND ilCl rlHlbSlUN.S DATA
Parameter
D.ite
Test durf. tion, tnin.
Stack Kas Flow K.ite, m3/mina
ft3/mina
Stai i Cas Temperature, °C
»F
Particulate Matter
Concentration, f»r/dscf
mg/nr
Emission Rate, nig /in in
k>;/hr
':ci
Concentration, mj;/ni3'J
Emission Rate, ing/minb
lb/hrb
Ku
3-1
2/12/86
115
45.43
1,604.0
576
1,070
0.00692
15.84
720.0
0.04J
1.07
48.3
0.0029
0.0063
n runiu"iar
3-2
2/20/86
240
36.41
l,i'.85.6
907
1,664
0.00332
7.60
276.6
0.017
2.68
97. »
0.0059
0.0129
3-}
2/22/86
240
35.81
1,264.4
871
I,b99
0.00479
10.96
J9J.O
0.024
i.29
40. J
0.0028
0.0051
Average
39.2?
1,384.7
7i>5
1,444
O.OObOO
11.14 I
4o3.2
0.028
l.toH
64.1
0.0039
O.OU84
aDry standard conditions ss during Run 3-1 are the results of
I test during the test run. Ddta from Uuns 3-2 and 3-3 are averages ot
3 tests durina each test run.
22
-------
TABLE i-U. POST-FLARE 5T.\CK GAS - SEMI VOLATILE MASS EMISSION RATES-
Dato
r./ 12/86
2/20/86
2/21/86
Rim if Co'^pOiiild
3-1 Naphthalene
Acennphthalene
Phtinanthrene
Fluoranthenii
Pyrene
2-Mcthvlnaihthalene
2-MeChyi/nonol
3-2 Naphthalene
Ace naphtha leu-?.
Phenanthrene
2-Methylnaphthalene
Dibcnzofuran
3-3 Naphthalene
Acennphthalenft
Phenanthrenc
2-Mcthyln.iphthalcf.c
DLbcnzofuran
Stack gas
ConcPitrat ion flow rate
('hig/m3) C-"3/niin)
'i5.40 45. A3
37.96
50.62
21.09
7.59
6.33
8.59
244.42 36.41
8.65
'-3.92
30.08
28.20
8.92 35.81
1.55
8.14
1.36
1.74
Compound Mass
2
2.30
0.96
0.34
0.29
0.34
8.90
0.32
2.33
1. 10
1.03
0.32
0.06
0 10
0.05
0.06
Does not include PCS, PCDD/PCDF irass omission rates - see Table 2-14.
-------
i'ABLh 7-14. POSr-KLArlE STACK GAS - CHLORINATED SE.'iI VOLATILE ORGANIC COMPOUND MASS EMISSION .
Stack gas
Concentration Clow rate
DJte Run -r l.oroaojp.r' (ng/n3) (m3/mir.)
2/12/86 3-1 nichlorophonol
Trichlorophcnol
Tr: c r ac *i 1 ? '•nohcno I
Pentdchloro|Jienol
Dichlo robe n zone
Tr Lchlorobttiizcne
Totrach Lnrobcnzono
PentacMorobunzcae
Diciilonn.itud biplionyl
Trichlor iriacod biphouyl
Mono-dec ach lor inatv?d
biph-iiiy 1
Hexaclilonnatecl
di.bcnzodioxin
rieptdchlorinrtdd
dibenzodfoxin
Oct.Jcnlorinated
diboniodioxiti
HGxn~ocC.ictiLorinatcd
dibpiiEodi.oxin''
Tet r-clil urinated
dibcns:of>..rap.
Pen each lor ina ted
dihenzofuian
Htj-zachlorinatad
dibenzoturnn
Hcptach1orinatcJ
d LbcnsoCura''1
Octachlcrinatcd
dibonzofur.i'i
TcL ra-octaciiloriii,-itc«l
d ibcninfuran
88.9 44.69
164.1
74.8
244.0
495.0
385.9
233.9
424.3
39.0
2.7
41.7
1.4
2.0
0.6
4.0
25.7
26.0
21.8
9.6
6.5
89.5
Conpour.d mass emission race
("ig/nun)
0.004
0.037
0.003
0.011
0.022
0.017
0.010
0.019
0.002
O.COOl
0.002
6.3x!0-5
8. 9xlO"5
2.'/xlO"5
17.9xlO"5
114.9xlO"5
H6.2xlO-5
97.4x10-5
42.9x.10"5
29.0x10-5
400.4xlO"5
(10-6 ,g/hr,
0.24
0.44
0.20
0.65
1.3.J
l.OJ
0.63
i.14
0.10
0.01
0.11
0.004
0.005
0.002
O.Oli
0.069
0.070
0.05S
0.026
0.017
0.240
»i.g»amt «v j» • m •
(continued)
-------
TABLf: 2-14 (continued)
(
Date Run it Compound
2/20/86 3-2 Xono-JecschLonnateci
bip'nenyl
?i'kat jchlor imted
dibenzodioxin
Itexachlorinated
dibenzod ioxi n
Hept.ichlorinatecl
d ibonzodie:iin
Occachlorinated
d Lbenzodioxiu
Penca-octachlor inatcd
d Lboiizodioxin
Tec each lor mated
d ibonsoEuran
Pen iacalor mated
d ibensofurnn
Hoxnchloriiuted
dibenzofurnn
IlcpCachlor Lnntcd
dibenzofur.in
Octacrilorinatort
dibanzofu-i nn
TeLra-octach lor inatcd
dibunzoCur.Tn
-one ont rat ion
(ng/rn3)
NO
0.2
2.1
4.S
5.6
12.6
12.0
18.1
26.1
39.5
43.1
138.8
SLdl-X %aa C^npOUP.d im •!
flow rate — ~ — - — •— — - —
(m /min) (mg/min)
36.^6 NA
0.7xlO~5
7.7xlO"5
17.5xlO~5
20.4xlO~5
45.9xlO~5
A3.8xlO~5
66.0xlO~5
95.2xlO~5
l4-'t.OxlO~5
157.1xlO"5
506.1xtO~5
-------
TABLE 2-14 (continued)
Dat«r Run # Compound
L/22/85 3-3 Honp-dec.acnlari.naCpd
bip'-ionvl
Pi'nta-oct ichlor ina^cci
r-. ibeir.od toxin"
Tetrachlcrin-itei!
dibenzofurnn
?0di^n^oCur.inl''d
Hsxachloi mated
dib^nzofurnn
Ncpcacnlorinated
d ibunzoCurnn
Octachlor inntod
dibenzofuran
Tecra-octachlorinafed
dibcnzofuran
N»
ND
4.3
7.6
7.2
11.1
8.S
39.1
Srark gas Compound mass
34.95 NA
NA
15.7xlO~5
26.6xlO~3
25.?:clO~5
38.8xlO-5
30.8xlO~5
I35.7xl0-5
eTiiss ior. rai.e
(1C"6 Kg/l>.r)
NA
NA
0.009
0.016
0.015
0.023
0.018
O.US2
'"Analytical data froa report received £ro~i /i-non Hnvi ronmcntal, Inc.
via Drs. ll-i^h ilibbs (Cl'S) and Thom.is Barton (PSI).
TfCr.'ichlorLnntcd diooi!=adLoxin noc detected Ln all Lliroc runs.
-------
plasma pvrolysis svstcm wnen firing PCB-conta in inr, liquid wasd;s was also
calculated for eac-'-i run s.id is presented in lable 2-15. Sampling and
•inMvtical Riethou* are described in Suctions 5 and 0, respectively.
In calcjlaciiiK the f'Rt for I'CH? Juruirf Kuns 3-2, c>nd J-J, an estimate of
the ninxinmm possible VCIi emission race had Co be used for cliche runs ber.iuse
the sample analyses yielded results below the instruncut detection limits.
This estimate uses chc sun. o'; t'ii; riinimum detection limits for mono throu,^li
iIec2chlc.rLn.irRd biphenylb. It is expected that rlu* actual HOo tmission rato
is fdr below rh
28 n f* |
5.54 m3 '
3b.-'(0 m3
ran
(>U -niii
hr
kR
I x I0l- ne
= l.l si IU~S k}-/lir
Run J-2
28 MS
3 . 14 in3
34.95 in3
in In
00 mm
hr
k«
I x 10 1 2 iv,
l.l x I0"l>
Where' 3'..46 m'/n-n = Volumatrn. flow rale ol stack KJS during Kun J-2.
34.95 <-./m\n - Volmpptric flow r.itu of i>tack j;as durinf, Kun J-J.
D.54 ir. = VoluPiQ sampled b; IltlS train durinj; Run 'i-^.
5.14 in3 = Volume sair.plc-d by M'li ti<"in rfurinj; rfun 3-J.
*IV-tr>ct ini limit ditn ohtriincil from Zenon Lnviroiimoiital, Inc.
-------
TA2U" 2-15. PLASMA HYROLYSIS SYSCf.M ORE FOR PC3sa IN A LIQUID WASTE KEr.
On t c
2/i2/ot>
2/20,'b-j
2'""»
Run :»
J-l
3-i
3-J
Run duration
113
2-0
21,0
Wast'j f
2
2
2
eed race
/n:.r.'
.10
.33
.20
PCB contnnt
(% weight)
li.3
12.5
12.8
PCB
input
IS.
17.
16.
mass
(kg/hr)
018
i>5
896
PCB mss
out (kg/hr)b
O.ll-.lO'0
'.~i of t'ncir detect ion limits for Ci-i - Cl-10 was usii1 Co
obtain .: tr.nxiniu.n possible H.Ti
-------
O'NCLiJSL0ciaie.l ML,
this rest program, several conclusions can lie irjwn. Mr-: a,v! lorcuobt, inc
ipcimolosv should be tre-,t.:r| as a promts -IIP. u.-.Hr8in». iccnnoloKV which sh.wld
jo further .lUKionsti.ieei! dunni; subsequent dial burn programs.
Th» notahlP conclusions vhich aro drawn iron the Its; prof-ran .in-
summariidd below. Those conclusion* are focused ,jn u.e denonsirjtion ui an
jrce-cnblc destruction and removal officicncy as delineated in i he UCRn «nu
FbCA rcg.K.itions.
o Kcsalf, frnn th,.> carbo-i tclracli lorj.Je c»sc burns imlicacc lhai Che
.-iy-JU-r ts capable oi il-st ioyjn8 a ",-iffi.uU co-Iostroy" KCn'
rcp.ul.iLcd waste. The DKKs fro,,. ,;aeh of tho thrcu test ourns
e>ccuded tiiu muiintiri RCM requirement of ^i/y.yy percent -cstrucrion
«ifl»cicncy. ~
•
1!C! emission ratios confonno.J r.c n,e ullo-..ib!c Uciitb of ;e troatmciu plant.
Ku«uli8 from tho I'Cll rest burrs uidicaff tr..-,t clio system is cjp.iole
o: ai-stroyini; a I'Cll l:r ; isn i LI cintly leus i Kin I n»-/l
Corrcspon.-I i IR levels in tl-e fl.ie A^ WOLO >,, LIIC rdnKc -I
J9 - 139 :K/nJ for tl,,> iot.il Lei r..-ocr .acnloi , no :od d DOOKOUU.-.,!
nln ind Ui) - 1^.6 nK/MJ for '.lu, tot ra-oc Caen lor I,M (...-!
o-p-d ionii.i'is.
-------
SECTION 3
FACILITY DESCRIPTION
The mobile plasm.i pyrolysis system, operated by Pyrolysis Systems, Inc.,
was tested while located on the ground? of Llie Xoyai Military College in
Kingston, Ontario, Canada. The major portion of the system was contained
within a 45 foot, specially adapted trailer, capable of *-.pinR transported from
site to site. Ancillary equipment, such hs the power transformer, wiste feed
blentling area, and limited w.- te storage futilities were located in a secure,
contained area within adjacei • Building 62. The flare and postflar-i stack
were located on the opposite side of the trailer from the building in a fairly
op*n area (Figura 3-1).
PROCESS DESCRIPTION
The PSI plasma pyrolysis process is based on the concept of reducing
(pyrolyzing) waste molr-cules to the atomic state USLIIR a rhennal plasma
field. A co-linear electrode assembly is used to produce the electric arc.
Dried, low pressure air is used as the medium through which the electric
current passes. Air molecules are subsequently ionized for.niiu; the plasma
field. Upon return to the ground state, the ionized molecules eniii.
ultraviolet radiation.
watte mixtures are inj«ered into the lield and interact with
the pi isma field. Tnis interaction results in a reducing mechanism in which
the molecules .ire atomized. Upon coolins, simpler molecules such «s hydro>en,
carbon dioxide, carbon monoxide, hydrogen chloride and other minor matrix
compounds such as acetylene and ethene ar«; forned.
PSI operated the plasma system and th? online analytical equipment. lh«
or'l\no system generated composition data associated with the product >;as
(pvur to flaring operations). t'SI was also rnsponsible for providing and
pr°.).irin« synthetic waste feed blends for subsequent testing. These test
were identified in the PSI (Duality Assurance test plan.
3-2 shows a blork dia«ra.n of tlin plasma pyrolysic- unit which is
the focus i:f this program. The systcn consists of a liquid waste teed system,
pvrolysis reactor, caustic scrubber, flar.i am! online analytical equipment.
C.iseous «£fli]i?nts fron the roactoi ;'=i.ss fhroi<<;h a caustic vunt'jri type
scrubber uhfni acid tno removal is i-ffi!(-r«d. Scrubber wntor discliari,e is on
the order of 32 liters pur minute. Subsequently, the product gas is Ilj-cd to
30
-------
BUILDING 62
OPERATIONS AREA
(BldQ. 62)
PLASMA PYROLYSIS
SYSTEM TRAILER
PREFLARE
PIPE
FLARE STACK
AND PLATFORM
SAMPLING
TRAILER
PARKING
LOT
PARKING AREA
BUILDING
BUILDING
ENGINEERING
SHOP
Figure 3-1. Facility area top view.
31
-------
FLOW DIAGRAM
PROCESS WATER
! FLUSHING FLUID
JC
CAUSTIC SOLUTION
~]
ELECTRIC
WASTE FEED
POWER
COOLING WATER
WATER SEPARATOR
(SCRITO.R)
OFF GASES ro PURE
SCRUBBER/
SFTiAY RING
REACTOR
.
r
EMERGENCY O'fiBON RLTER
GAS CHROMAf OGRAPH -
M/vSS SELECTIVITY UNIT
LABORATORY
ANALYSIS EQUIPMENT
GAS CHROMATOGRAPH
DISCHARGE tO DRAIN
Figure 3-2. Process schematic o-f the PSI plasma pyrolysis unit.
(from PyroLysis Systems,
-------
complete thp cleat. up cycle. The post Elsro gas then enters the st.ick and is
discharged at the approximate height of 8 meters above grade.
V e nominal treatment rapacity of the system is A k»/rain of waste feed or
approximately 200 L/hr. Product j;as proc'uction rates at this operating '.evel
-iiv on the oriier of !>-6 n-'/min prior to fLirinx operations.
For the purposes of this test program, a flare containment chmbi>r and a
stack were included to facilitate testing, ttfter conbystion, tin: flue gas
flow r-ite was rn the order of 36 m /rain ai standard conditions.
3J
-------
SECTION 4
SAMPLING LOCATIONS
The locations for collecting che various sample types are shown in
Figure 4-1. Ihfi locitions remained unchanged from the original Quality
Assurancp Project Plan with one exception. At the preflare product »a*
sampling location, difficulty was encountered in obtaining representative
samples due to vt-iv hich carbon loading and entrained moisture. Additionally,
during several system upsets, hydrogen flarebacks occurred creating a safety
h«/.*rd at that location and caused sjnple probes to be blown out of the port.
No further tcstinR took place at that location.
IMSTE FEED
The waste feed was -aamnlcd downstreaii of the blending and pumping
operatio'is through a valve assembly just prior to entering the reactor feed
rinn (FiRure 4-2). The feed line was under pressure thus enabling an
integrated waste lead sample to be obtained during oach test r.in. '
RHACTOS AS!I
Reactor ash was sampled froii the interior of the reactor. Because rh«
entire torch assembly, cooling water jacket feed rinfc, and grapuite core l:ad
to he reaoved to .ic^o-aplish this, ash samples were taken only when available.
SCRUBBEB 1,'ATER
Scruobor water samples were obtained at the discharge point of the drain
hose as shown previously in Kij;ure 't-l.
POSTFLARC PRODUCT GAS
The stack is constructe-1 of 1/4 inch stainless steel plaLe rolled to an
I.D. of 16 inches. The flare containment vessel is similarly construcLed, but
with a 43 im.li to a 16 inch I.D. taper, heyinninR approximately ?l mches from
the base. The flare head, constructed of a 4 inch stainluss, steel elbow,
protrudes into the uonLaiiinent vessel where tne reactor product Rases are
iKnit«d. The flare is ISP! f-sustaim n«> and could tie ignited either remotely
with an icnitor fixed in place, or manually, by piscine the ifinitor into
position until die flare was lit anti then withdrawing it. It w.-js found that
the latter w.is th.: more reliable .is Lhf.- igniter w,jd nrt continually subjected
to the vibration and extremo hij.it present at the flare head.
34
-------
o
POST FLARE
PRODUCT
GAS (4A)
(-SB)
1
I
PLASMA
ARC REACTOR
®
WASTLhttU REACTOR HEARTH AEH(2>
WASTE fEED
SUPPLY
1
1
/ — '
PRE FLARE
PRODUCT CAS (5
VENTURI
SCRUBBER
~ 6
SCRUBBER
WATER (3)
DISCHARGE
ling 1 oca Lions,).
(-Deviated Co
35
-------
TO WASTE
FEED RING
d
VALVE
ASSEMBLY
1/4" LINE
WASTE FEED
PUMP (POS. PRESSURE)
TO SAMPLE
CONTAINER
4-2. Waste feed sampling location.
-------
The Clare stack was designed with rht flare containment vcssf.l to allow
tor the rdpid expanoion of the combusted reactor product gas. The vcshel is
open -it the base with an opening arr>a of 1.17 square meters (12. DO ll^) .
This opening, in conjunct ion with the rapidly heated gases;, allows tor P. flame
and stack gas buoyancy which eliminate* the need tor ia-luced dratt or forceu
draft fan. In spLtf of tb«: lack of a fan, once thr- flare is lit and
temperatures have stabilized somewhat, the gas tlow rates through the btacK
are also rclitively stable. There is the presence of temperature spikes at
times which is usually attributed to re-entrained carbon at the flare head or
nu hydrogen content of the reactor product pas.
Poocflsro product gas samples ware t.iken from two locations downstream oi
the flare. The flow di.igram in Figure -i-l shows these locations in rela»-ion
to the rest uf (.he process. Figure 4-3 illustrates tl>e postflare stack
configuration and samr/ling port locations with their associated measurements.
It should he noted that, 1 1 though the sanpling location for the hM5 trains
satisfied the 8/2 criteria for laminar flow, the small diameter of the stack
(16 inches), in conjunction vith the number and Lvpes of sampling proofs
required for the program, is not conducive to ODC. lining accuiate flow
measurements. Ti,e hij;h tempera rui-es found in the stack r;ecasoi tated the ut,e
of water cooled probes for the MM 5 trains. Two MM 5 trains were required by
the Administrator to be run cinult ineously in order to provide separate
I'CU/Dioxin nnd semivol^t ile 'Jamplps. The 'jlocka^e raused by these probes
dlona approaches 22 percent. Further flow disturbinces within the stac-c could
have been caused by the otl:er in-scack probes situated 7? inches upstream of
the rfater cooled probes. However, in spite of the blockage a~ -\ possible flow
disturbanTes, tho velocities and flow rates Mp.-i-iurec! by both ' rain.i rlurinj; all
tlireo test runs '.-ere in clos<> a^ree....int (./ithin i> percent", ihe
point* for all trains -u« illustrated in i"ij;uri> b-^.
The HCl nnd VOST s.imple probes were located 'i.7iJ diaaeLers downstreira oC
tot! flarf- cnntaianent vessel. During thu CCl/, burns, tho. CliM probe and
filler were colocated with the HCl probe, .is there w^re no VOST runs required
during Stage II, Test Series 1. The CC1/, inlrei; rated ba« sa-npling systems
were set up on the sampling oi.itjrorm and sampluij; was conducted from otic- of
the uppet po'ts.
During Test Series 3, the two hM5 trains, as well as the CEM probe and
Cilter hotbox, were net up at the upper ports, 8.2« dia:neters downstream of
r'.'e flare coni:aim.-,"nt vessel. The CEM probe was bcrit -it a A3 decree angle in
ord^r to eliminate interference with the MM5 sampling probe in port A. The
GEM probe tiu remained on the same horizontal plan as the MM 5 no/zlus.
PRFFLARi: PRODUCT GAS
As mentioned earlier, samnlinj; efforts at r.f.is location were aborted aue
to unsafe sampling conditions and ve ty high carbon loading and IT trained
•nnioture. Th.» st.-iinle.'.5! steel pt'<-jflaro pipf exits tliR trailer approximately
eii;ht (3) f«et off the Kround, '..ikes a downward hund, and then I-IIUM along the
gro.md aijoroximati-ly twenty (20) feet before takinr, a 90° upward b-jml tn form
37
-------
MM5 SAMPLING
poms
Loo"
_L
CRATING
oTACK ID.- 16 INCHES
NEAREST UPSTREAM DISTURBANCE'
8.2B DIAMETERS
NEAREST DOWNSTREAM DISTURBANCE.
A&ti DIAMETERS
-MCETS 8/2 CRITERIA
78"
CEM &1.U.-G
PORT i
VOST/KCI
SAMPLING PORT
132.:;"
60S"
I
72"
FLARE
4-3. I'o.Tflare t-mission snnpling locations.
J8
-------
MM5
PORTS
HCI/VOST
PORT
(single sample pomt-6")
MM5 SAMPLING POINTS CA&B PORTS)
DISTANCE TRCM
POINT _J^iM-_Iil-J_
6
3
2
0.70
11.26
13.66
: 3. jfl
Figure 4-4. Sampling point.
39
-------
the Ha-e. Th« icnitor was originally a permanently mounted spar* source, but
has aLnre beun altorec! so thai it lias to be manually o-iL i'lto place and
removed durinv; the iRnitior. sequence. 1'he pref 1.arc* s-vnp!*- ports ware located
90° to each otli«r in the 6 inch stainless steel pipe approximately ten feet
of thn flare. The he.ivy, moist carbon present in th« preflare
&ns caused pluKKinf; of the sampling e
-------
SsiCTl'iN 5
SAMPLING
Ihe orocodurc, for obtaining sample-, of die wasce teed, .-c-actor as!.
scruober water, ami postflare stjclt g,,8 arc described u thu, section, 'ii.e
methods ur.Pd in sanplin,. renamed essentially unchanged fro. those described
in die Duality Assurance Project Plan submitted lor this program. i,,y
deviations from the described methods are called one in Section 7. All
containers used in collectins and/or stori,fi these samples wore prepared as
stated tl, the (JAIT. A summary of die sampling methods used
WASTi: FEED
Liquid wastes entcnn,; Che plasma arc reactor enter by way of a -nachined
""*• The waste fecd is
... •• -" K«-i|"--i Hum i. nc a i uras LH wnicn ic is
blended, through the calibrated rotaneter, dm,u«h the stator pump, and into
the waste feed nnfi. Just orior to the feed nn8 is a 'T' connecti»n and
valve assembly which allows a samp! to be taken under positive pressure. T,,e
valve allots line adjust,,,cnt of the liquid flow ,0 chut an ,nteKMrua sa..,PU-
can be ., Ea«»n over the duration of -ho test run. Waste feed samplinr
corainenccd after the systore w.is switcncd over to the desired w.isic- rood
U.e.. CU4 01 PCit, depcnduiK on the burn schedule). mis ensured sauplin-
only the ••uv.et wast* f«d .ind not the flushin,; solvent blond U.e., MrK/MLL-i)
If a system upset occnrrcd durmR the s.i,npl,ng .un, neccssitat inK ^witcn.ng
clt 11,4 t^rsel waste iced , the la-nple valve was closed and nut reopened until
Che target waste iced was switched i>ack on jnd LI was tell that tutticicnt
volu.n-' had p^sed tnrou..h to d.mimsh any effects of dilution ny the fl,,bhnifi
solvent blend. At the tnd of each test run, the wJSte ieed samplos were
return-d to .1 ,.aate feed .Irun, after obtainim; die required al;r|UOcs ul the
liquid Much were then transported to /.enon Li,vlro,,n,ei,iai, Inc. tor subsequent
analyses. OG\ also arct-wed waste feed samples from cacn test run.
RKAC10K IILXKTI! AbH
Ash ,a-nple, wens not taken ..mi a,Mly/ed bv CCA. i,0,e 8Oilpies ,C carbon
-oi,nd deposited on cl:e .now JlOui,n the Llack area wte collecto.i for ,,Vbutc'to
»
-------
SCXLTURI:R WATER
The scrubber water s.imples were composited in .1 ll) liter ja- every
30 minuted during each Ccsc run. I;urir>a cadi srali sampling episode, Lvo
10 l-.ter simple jars were transported Lo £enon for
analyses for PC3s .ind W^OUs/PCliys. In nil compositing efforts, trw tcruDtwr
uiter was nixed thoroughly ro ensure a representative cartion/aqueous solution
mix. During some s.tmpluv; periods, the amount of corbjn prcaenc in the
scnihber vittur ua* noticeably l«s& than at other lirarc.s.
FOSTFLARE STALK GAS
Table 5-1 sur larizeg th«i sampling r>iPthoJolo>>i<2S utilized 1.1 tills program
to character v^e emissions from cho pyrolysiti systeia while pyrolyzinj; two types
of ehlor^n.Ttfld water fcetls anil flaring the product gas.
Itnl k
Continuous
A continuous inonitorinj; syscum wa-s in operation durinx the two test
serves of the project to monitor conoe-:trat ions of CO, U », C02, an»i NOX
in the tine gas. In a4diti.ni., continuous fipnsors for nieas'irinK post£l>
flow rates werit inclnHiid during Llin CCl/, hums, /ui attempt to nonitor flow
rates qnd temperatures 4t the preflflre loc.H.ion was ahort-d due to Cdrb^.i
pluuainc and tlie hydru>;en flarebaclcs. Tin; inonltorin^ systeia «.-js comprised of
3 RSS cori'iitLoninp s.-itnm, for meas'jrinj; CO, 0>, COj nncJ i£ax .ind a data
acquisition system as shown in FI^IJTB j-l.
rim R,?S conditioniuc syatam consisted of a i;las:j fiber filtr.ition uiLt
mountod on the probe to roniovij part iculatcs ^nd a conn rhu flins R.IS. Thi- final seep in moisture teraoval is
acliifivod by :in inline ptimvition dci<:r. Sample j;a.s exiting the pcnaeat 10-1
drier Ls then ready for .in.il ys is. Cn.t analyses will be perforned usin^ the
•Instrument a described in Table 5-.J.
Carbon monoxide concentrations were 'iiei-iured usin,, a lioriba
PIR 2000 NluR Analyzer in the operating r.in,{<; of U to 0. I percent full scale.
Calibrations preceded and succeeded each tasr. hy injectui)» the .ipprupriate
zero and soan
concentrations were mcasur*!*! usini; a MSA Model SUJ 0^ Analyzer
in the opi;r;itin>; rant;c 0 Co 25 percent full scale. I'iii! •inolyzer "as
calibrated b-Ttor^ and afcer ^acli ti>st with .1 ^ero j>a.s of ultrapure
and calibration spin fj.tycs of the appropriate concent tations.
Carbon dioxide wn neaj.srud usin^ a Jloriba FIR 2000 KiJiti CO^
in the oper.itinu rans^e 0 Lo 25 percent f'lll srale. !''ns analyzer uas
calibrafd before ind after ^-acfi lust with the spplicjhle xern and span );ases.
-------
I \SLr: 1-1. PKLTLAKfc AM) POSTKLAHE tlllSSIOK J'AkAMhTKkS MtAblikfcNI.VIb
1>ar3llluccr ColU-cCLin niclhud
ors (1V.CB Meilioci)J
Vol.-,rLl« Or,:inic8b InCCKratcd Fcdlar Ba,
Volatile Organic Sampl m;1. frain
(offsicc analyses))
Senuvol.ii-.iUs Hod if led Hetl.orl 5 (MMS)
PCHs Hodificd Method 5
PUW/ITUK Modified Method 5
in.itr.er Mo,,rm, Wj-;i llicd uur.n,'
endurance burns. -1
-------
PROBE
i-'IT CH-
UG
CALlBSA'nOfl
•'• G/.SES
(CO ,Ct .'".DT .Ndjj,1
ic-0
50, SPA'i
•>V 3 ?••••.
_J
\
S.-ii'LC
OliTSlRjTIO"
'SV-Sl'!.".
! .' SAMPLE
?. LOCAL
TIOH5
:•. ff.SZi
•
C.ALI3SA-
fL'J'lE 2-.00.-/I 7:0»
••CCUiSITiQri SiSTCH AND/OR
."A.'.UEL C'fART HECaso'tP
Figure .5-1. Continuous -monicoring sampling schematic.
-------
TAbLE 5-2. CEM SAMPLING PARANEFLRS ANU ME
Available
Parameter Instr-.mcnt n-odel (detection) (up to)
C0 I'oriba I'I'c 2000 (Ni)lR) i)000 ppn.
°2 MS*1 Model 802 ( ParjiiMgnctic ) j^
co? Horii-a V1K 2000 (Ki)II<) 25/
K0x TPCO Midel IOA (Chemiluininescfince) 10,000 ppni
Velocity Rosemont Instruments 5 inch I.1.c. \'
-------
Oxides of nitrogen (NOX) were measured using a TECO Model
Chemiluminescent NOX Analyzer in the rango of 0 to 1000 ppi. Calibration of
the analyzer was accompl ished using nilrop,on zoro gas and span Rases of die
appropriate concentrations.
Continuous monitoring of Llie flue gas was performed according Co I lie
following sequence:
I. Arrived onsite, inspected condition of equi,.nant.
2. Set up and leak checked conditioning system through manifold.
3. Connected all four analyzers to the manifold and data acquisition
system.
4. Performed initial- calibration of nil monitors with zero, raid and
high span certified Rases. Made any necessary adjustments on the
monitors.
5. Monitored CO, 02, C02 and NOX throughout the flue gas testing
nuking sure to ra-irk the strip charts noting the beginning aid er.o of
the test runs.
b. At the and of each run, recalibrated the monitors and noted all
values on the appropriate data sheet to deLumine nonitor drift.
7. Mom Cur ing data wore reduced and presented as .iveragt: concen (.rations
and, lor CO and NOX, hourly emission rates.
The continuous uoni tori p.p. system inspection, installation and operation
was performed in accordance with the applicable instrument manuals.
Flue Gas Molecular Ueigut by Integrated Orsat--
Ttie flue gas molecular weight Ls required by TSCA and RCKA to be
calculated from data representing each sampling point in the stack. Because
the Cf.MS was situated for single-point monitoring, it was necessary to
calculate the molecular weight from the average of the data from the four
1-hour integrated bag samples takun during each run. During Kun 3-1, it was
only possible to obtain two 1-hour samples due to tne shortening of the test
run. A lung sampling syste-n was used to collect the integrated stack gas
sample in a Icdlar ban. This system was leak-checked before and after oach
sampling run to ensure no leakage occurred during the run.
Trace Cases
The trace gas samples wove collected from tne postflfire stack and wer.-;
analyzed for HC1, s<>niivolat.ilr!S, and, iioru specifically from c!;c Idcter group,
PCBs and PCDD/PCUF. Carbon Letrschloride and polychlorinatud biphenyls u-ere
introdured into the plasma arc as separate waste matrices during the two Lest
etages. The capability of thu plnsna arc syster.i to either destroy or remove
the target compounds were measured by the methods outlined in this subsection.
-------
Volatile Organic Sampling Train (VOST) —
The VOST was used to collect VOCs present in the product flue 'MS dunn«
Che Ion* term endurance runs. Vi)C refers co those organic compounds with
boiling points less than 130°C. The method utilizes Tenax and Tenax/lharcoal
cartridges each of which is preceded hy a condensing modulo to adsorb L. e VOCs,
The train consisted of a glass-lined probe with a glass wool plug to
rpaiove particular, followed by an assembly of condensers and organic resin
traps as illustrated in Figure 5-2. The first condenser cooled the Kas strcdn
and condensed the w;iter vapor present. The flue gas and condensed moisture
then passed through a cartridge containing 1.5 grams of Tenax resin
(60-80 mesh). .n« conclfns.ite »ts collected in the first iinpinger which was
contin.ially purged hy the gas stream. The second condenser and Lrap
containing Tenax/ch.ircoal served as a backup for low volume breakthrough
compounds. Following the second Tenax trap is a silica >;el drying tube tor
rosidu.il moisture removal. The sampling train was operated at * tlow race of
0.3 liters per .ninute and the total collection volume did n.ot exceed A)
standard liters.
Sample temperature was monitored at th« outlet of the sample probe and
the inlet to the Tenax cartridge using thermocouple s. Hie gjs temp-jraturc
through the probe was maintained above 150°C to prevent the premature
condensation of the volatile components. The temperature of the gas through
the resin cartridges was maintained at less than 20°C.
Extensive sorbent preparation and Quality assurance procedures were
instituted to ens.ir-i the integrity of these samples. AH components of tl.u
system coming into contact with the samples were rinsed with Dl water and
dried in an oven at 150°C tor a period of i. hours prior to use. The Tenax
adsorbpnt and glas- wool packing were precleaned as described in the Uialitv
Assurance Project Plan.
The presampling preparations for the VOST included:
e Mashing the train and .sample containers osinj; the following
sequence: soap and water, prc-extracted DUI water rinse, and
methanol rinse.
• Pr.jp.iring VOA vials for condunsate recovery which were not solvent
rinsed but were heated in an ov«n at ILO°C for 2 hours.
Setting up a field biased blaT'x stapling train which was
dis issembled and recovered in the same manner as the actual VObX
following edch run.
Collecting methoa blanks of 1)1 water, Tenax. and charcoal.
-------
HEATED
SAMPLE
PROBE
3-WAY
VALVE
ICE WATER
CONDENSER
TENAX
CARTRIDGE
CONDENSING
IMPINGER
U//AI HjO
ICE WATER
CONDENSER
Figure 5-2. Volatile organic sampling train schematic.
-------
The recovery activities for the VOST included:
• Removing VOST fn-.:n sfack and transporting no ne-jrby recovery are.i.
• Sealing the sorhP.u cartr;dj>es witl- teflon tape and placing thmn xn
their nrigiraL r,Uss culture tubes with glass wool to absorb shock.
Measuring the volurae of Lhe condunsace Lnpinger witli .1 predefined
cylinder.
• Transferring th* nieasured conc'ensate volume to 40 ml. VOA vials and
diluting to volume with UI water to decreasp. headspace and tho
possibility of revolat i liaat ion of thu compounds.
* Further reducing reactivity by storing all sanples at 4°C.
The samples which wer? collected durin« each VOST run consisted of a
Ten-ix cartridge, a Tenax/charcoal cartridfie, and the product *as condensate
(captured by the mini in,pinfter). All samples w^re labeled according to thoir
series number, run number, sampling train typo, soling component and
parameter to be analyzed for.
Leak chocks on the rabled an.J reassembled
d.:nn« a test run. Tho sample tr-iu, leak ch.:c'au Sampling for VOCs—
For the purpose of onsito analyses for the target volatile compounds
durinp. l-hour CCl/, burns, nn inccxrated Todlar bag collection method was
utilised to collect tho samples. A nyrinj-e was th.-n ,,.sea to draw * sample
from the bag and Inject onto the UC/£CD column.
The baK samples were collected on an hourly basis and analyzed for VOCs
onsite by UC/ECD. One baj> per day wis filled wlth prcpurified :<-, for use as
a field-biased blank.
rlh.! gas bar, samplins; assembly cmnlnyed is shown in Figure i-J. it
consisted of a cleaned, evacuated l.-dUr bas placed inSlde j rifiid container
that was evacuated at a known ra'e during thn sampling period. 1'rior to
sanpline, Tedlar haKs were pur>;od with prcpnri£i«d nitrogen and evacuated.
After the sample, was .Ir.Jwn, a guick-disconnpct valve atop the container scaled
the sample in the b.ig. for direct anal/sis.
Leak checks on the int.jftrate.l bai- sa.nplinj; train were pcrforaed bclor--'
and aft^r each namplit.K run. The sample Lrain leak checks and lcakaKe r,Ife"
(if applicable) .ire t'ocui'.enced on the field test data she^t tor each
run.
Modified Method 5 OiMJ)-—
MncJified Meiho.1 5 jamplini- trains were use.l for t\w collection of
pi rticulii.es, .vnivnl.itilcs, polyohlorinated biphenylb, anJ polychlonnate.i
-------
STAINLESS STEEL
PROBE
-TEFLON LINE
Ul
o
i r—
GLASS s—
CONDENSER i_-_
^». I 0 Cf^n
ii j\i i | i i'j^j
U
i
~
li
I
J
TO PUMP
L
CE BATH
I
TEDLAR BAG
Figure 5-3. Integrated gas sampling train.
-------
diben:-.o-p-d loxins/polychlorinatiii! dihenr.ofurans (PCL'U'l'COF/. A schematic or
the M.'IS sampling tr-ain is shcuii in Figure 5-4.
Additionally, a tie Id-biased blank was set up at tiie site for each
pdraii'L'Ccr (i.e., one cc.TUVcl.iCilc field b'.auX., one i-Vd iiela olinkj Uurii.t;
each test flay. ll was set up and recovered exactly Che same way as the acLual
.sample Suit without liavin» had sample nas flow tliiough tlic system. Tnc
field-biased blanks were treated analyt ici I ly the same way as actual samples
and the results will provided appropriate blank corrections.
The sample train consisted of quarts j;lass-l ined heat-traced water-cooled
probe with a:i inconel button hook nozzle and attached the nnocoup le anu pitot
tube. Vhe probe- VMS Maintained at a ter.poratnre of HSO'r" _•_ :'.5°l'. Alter tne
probe, Mi.' gas passed through a heated glass fiber filter (Ueeve Aiijjel VjA All
filter ,1.1 por). Downstream of the heated filter, the sanple nas passed through
a water-cooled module, then through a soruenr module contain my approximately
2'js. of X/VD-2 resin. The XAI) nodule, winch was ";cpt -U a teiiipcraturti below
2(.'0C, is followed by a series oC four imp infers. The first inpinser, .ic LeU jn
a cond^nsatc lesorvoir connect to the outlet of tbt- X/ii> nuilule, and was
raodifiud with a short stem so that the s.nnple gas, d iu not oubble throu/n tiie
collected cond^n&ate. ITie first and third impinge rs were empty, the second
confined 100 tnL of DI water, .mil the fourth contajnuu a known weight of
silica gel. All connections within the train wen.1 >;l.iss or Tetlon and no
sealant greased were used. Tnc in [J infers -vc.'.e followed by a puisiu, dry jjas
mct«r, and a calibrated orifice meter.
Ri:idi!if,s of flue j>as p-iramelerj were recorded at every sanpl my point
d-iiinK the sa^iilinj; traverse. In the event Lliat htcaoy opcrdtion uas not
ma int.nncd , or Lhote were atypical flue in -it ions in inonilorecl ^as paia'i.ulur.s
(C(J, 02), the testing was stopped until th*&o conditions were stabilised.
Steady operation of Ine pyroUiis unit w.it> the rcsponsioil ity ot fyrolysib
Syf.tems, inc., personnel, but the flue gas parameters and compos it 10:1 was
monitored by OCA. Any changes were noted and relayed to i^bl personnel io 'Mat.
appropriate action could be taken.
Sampling was conducted while 1 1 PI/C rs »m> the- MM5 train across tne two
I'ianeters shown in Figure 5-5. The slack satisfied the S and J. criteria for a
nun'ier of samplinr; points aid a twelve wnni tcsn. was selected for
runs.
1'rior '.o sampling, -ill pis-contacting co.npcnont.s of the train were wished
with alconox ^.id water, tliorou^h ly ringed with Lil water, anJ oven drieo at
110°C tor .it Itast I hour. immedintely prior Co use, the i < mpoiiont s were
rinsfd with lipx.-.ne. At each Lest point within the stack, all neces.s.jry train
parameters i.-ero measured. All fiel-J ; train tere pcrforuua li-itoie dnJ .uier
(•ach s.impl inc. run. The sample train leak cheer.*, and leakage r.-it.;
(if applicaole) ^cre documuiued on the field test data siuiut lor L-acli
run.
51
-------
UNGREASED
FITTINGS
PROBE
a TACK
WALL
HEATED
FILTER
REVERSE-TYPE'
PITOT TUBE
4
FLOW -'
THERMOSTATIC
WATER BATH1
I ^1
PITOT
MANOMETE
i
r-THERMOMETER
CHECK
VALVE
K fi( fertlfc:
THERMOMETER
o
ORIFICE
O
_ r
"• !
i
ORIFICE!1
MANOMETER
Figure 5-i. Modifiud Method 5 tiMin.
52
-------
;
65 4
— • » e- _
5 2 1
» ^ «, —
1
l
03
92
Distance
_fron '/.ill (I
0.70
2.34
A. /i
11.26
13.61
15-30
jSure 5-5. Mr-d.fii-d "otlinri 5 smp.'t point locations.
S3
-------
Following co.npleti.on of each test run, the MH5 trains wore transported to
the onslie trailer for recovery. Recovery procedures diftcred depnnJin;; o;i
whether the 4-hour MM5 samples were to be analyzed for i'CUiVPCUt' a:id i'Cds or
siiauvolii, lies. The PCDD/PCD!-' and PC3 train was analysed solely lor those
parameters and not for part iculate emissions. Tho recovery procedures
outlined in the Quality Assurance Project Plan ware followed.
llecausr; the participate catch from the Mft3 trains intended tor
scitiivolaLile CC/MS analyses were to be first used to de te r.n i ne jjarriculare
piiission rales, a slightly more involved recovery procedure was required. Tr.e
recovery technique was conducted on those 4 -hour !1M5 runs not intended for
PCDD/f'COF .malyses. The procedure followed during this recovery was as
outlined in the Quality Assurance Project Plan.
Affr tho total narticulatp catch was determined, the acetone rinse
tesi'Jiie wasi reaisnolved in hexani: and die organic analyses proceeded as
described in the dii.ilyric.il section of this report.
Filters for all modified Method 5 Lr-iins were tare-weighed prior to use
for the determination of particulate loading. These filters were then placed
in sealed class containers Lor shipment Lo the test site.
Sorbent resins? used in MM5 sampling trains require extensive preparation
and quality assurance Measures piior to use in the field to eliminate the
posalhilitv of sample bias due to sorbent contamination. Tlvi XAJj-2 resin used
in this sample train was obtained from Supelco, Luc. The resin was precle.ined
by sox!il«>t ••xtr.Tccvon usinj; ihe sequence outlined in tiho ir.iU.-kTP Procedures
Minimi: I.ovel I Enviromienta I Assess:m>nL as described in the l^j'ility
Assurrinrt- I'rciject Plan. Tho X/JJ-2 resin used in the MMT train for i'CUU/PCuF
collection was soxlilet extracted overnight in toluene in iddition to the
ce outlined in the IERJ.-HTP Level I .issessmei't procedure.
Gisi>nus HCl —
Sampling was conducted at the posLtllaie sampling location to quantity I1CI
emissions during each sta^c of this test program. Ihe met hod used in
collectinn the ga^uoun HCl was the Texas Air control Hoard ( I'ACIJ) m.;thod with
deioni/.ed water in the first two imp infers as tne absorbing solutions.
The samplin,; train is shown in Figure 5-6. It consists of a pcobe iin.:r,
an Lmpinger train with DI ll;>0 and silica gol, ••=. punp, a Jry f;as ineti-r, and a
in-uiometer. Chloride was determined OISILI. colorimtit rically Jiirinp, the CCl,t
burns. After the A hour i'CB endurance burns, the samples were transp^rtea
b-ick to OCA for inalvsis.
Leak checki on the HlH sannlin^ train were coneuct^d befori; and a' tor
each innplin^ inn. The s.mple train leak checks ana le ikat;e rate
(if anplicabl") .-,r« docusif nted on th-j field test data shi
-------
SAMPLE PROBE
II
1
1 1
1 ,
II
t_J
i
1
I
L
i
ABSORDING SMPINGEKS
VACUUM
COARSE GAUGE
UMBILICAL
i'i};urc 5-6.
!ICi
;: train.
-------
P (IhO) —
Moisture in chi- oostflari stack x-'i'' was determine.: ny un,,in:;er
Rain from the beginnine of the test run Co the «MU|. ia Eluii method, initial
and final weights of tlif: unpin;;ers are obtained !w we-.Kib,iiij; on a Balance
accurate Co O.I gram.
inri Flow Rates —
tin: I hour CCl^ t-ist runs, .1 pressure t ransikict-r .imJ
tln;pi!oconple wr-r« us°d ro continuously inoi.Ltor stack ;;as velocity and
tenperatiires at tlic posLllare location. Monttorirg tin: y reflate location was
.j'. tempted during che first CCl/f burn but was aborted fofiBowinK several
flarehacks in thf piefL.iro pipu as well ns .;/.i-j;rionc mr. heavy carbon
of the pitot tube.
Fliw rates, anil tomperaturus during Hi..- 4 tiour IJCU endurance tesr. runs
w«;r
-------
SLC11UN &
ANALYTICAL Mf.ThOUS
'llic :ollnwin\; sere ion iiol i;iaatr"? tiic. an.ilyiicjl protocols wiuch weio us
to analyse. -..-iniplcs in the field a> wu U ds the OI.A i -ibnr.iLury . /.s u it,eu-,S(.-o
in eaniir sections, the followin.> process) scn:.i,;:s woo- sinpl^il:
• Wj'itc Feed
o KcacLur Hearth Ash
• Spent Scrubber Mate r
« Post Clare 1'roduct Gas
WASTi: KI.CD AND SCKL«6BL'rt WA1LR
Vo 1. it i I f Hri'./in ic C'iipDnuii<|q
i'lfiiit pjinplfl., for Vi)A .ui,-> I yd is uur«- collc.Luil in iluji I ic i to. W.T,t-j :"«•.•.!
s.inr l"'i wcrp .ircnivcd. An.ilyscs of j'jueons -..inpivs wo i o coiuiucl'ju us 111,4
cor.vnt.ion.il ini:i;c ami tr.ip 'jC/tlb pructiriurus in .iccorJ.iiu-ti wun LI' A
Motlioci ft}!*. Sn: !ot;.itG spines cons ibr in,", of dy-toluone,
d/.-l.I-ciichloroftliaiK*, and lironof luoro!>«*n/.cnu, wore jiicK'd to jll u.n.i|>U-s .is
described in Section 'j of tin: (Jualicy Ass-rjncc Project I'l.in. Aiuly^;. wore
con.mctiid us it!/; J Kuniij'iMi OVA =fxiputcri/.ea gds chruuiaLov,ra|>n/innss
spect rtpir.ctcr. Priority pollutants WIT« idontiiicd by coi:ipuLer i-iitii 01
retention tnr.es and 'ipectrj of H t.indar'is deLe mined un LiiaC '!->• .
Thn idcnt i licjlinn of .ii'.dit : iu.il compounds iiutoclud by tlio i^L-H-S syst'.in
wi-rc iletcmmod us in« a cour.uU'r suarcli of tin: Nbb/Lr,i>lalt library to (-.
Cental I*1-* -ipeccr-jl m.itclins. Ihci^p, js \/oli as unknown spectrj, weru ruvi
for major pi-ak:. .iiid f i an-nfinl.il ion fulloriib. '-urLlier ineiil il icai io.ir> uori"
by the orvr.ilor .in>l vt-rifi'--1. bv conpnr:jmi of .iv.nlal-le ruiorcncc sfxCttrd
('JBS/ I.PA/NI II linrjry) to tl'C b.ici.j-.rounii cortoc tt.*'! coiipn:;unL spccLro.
(ni:. rmir.nl roncont ul :o:;r wore cjloulai-'d relative to • no rlo^csi tiluiir.,;
I.UITII^. I «:t indanls. /.I I valuer, represent. .i|jproxinii.iiui\& -Ji-d to inii^tui!.
v.irtabil ir ics in coipponcnl .jsponse faclns m- ti.o .ibsi>ncc of ramrenco
ir.a tf.-ri.nl «•.
r>7
-------
The To I lowing seeps were taken to detect contamination introduced in
sanple handling or analysis:
1. Analysis of field biased hlnnki.--Uci.on ized water taken to the tield
anci carried through the storage and analysis procedures wer«
analyzed.
2. Daily analysis of method blanks—A sample of ^ionized water was
analyzed. This detects conttimnation introduced oy the pur^u yas or
che tubing in front of the traa.
3. After analysis of a liiRh (->200 j^b) level sample, a blank ot
deioni.:ed wjter wjs analyzed to ensure that contamination ot
subsequent sur.iples by carryover had not occurred.
Semivolatile Organic Compounds
Aqup.ou3 samples collected For scinivolati le organic conpound determination
w<:re analyze.! in accordance with b.l'A Method b25. burror.atc compounds were
aii.Urf en the samples and tlion serially extracted with metliylcnc chloride Jt a
pH fircater than Ll .n.d a»«in at pH less tnan 2, usin» a separarory funi.el.
The. niethvlene chloride extract is dried and subsequently concent rated to a
volnr.e o( I to !! mL. The concent rated extract is thon analyzed by ^.-5
chroma tor.r.iphv /mass spectrometiy . Part ioulato matter was separated t rou
a(|ueoiis samples \ia filtration and subsequently extracted with 3 soxliLuc
auparatus usuii; uu-tliylcne chloride. 'flic extract was then subjrcted to
concentration and >"C/!:3 .inalysis as descriOfd for aqueous aliquot^.
POSTFLAKL STACK CAS
Modified Method 5 (for Seni volatile Uri;anics) —
Metnod b train samples were analyzed j> (JCA for s.enivolat i le orj,Jiiiv.
compound1;. Each train, as noted earlier, produced foui types of samples:
1) partic.ilate collected on a filter; 2) probe rinses.; 3) X-vU sorbt-nt sjinples,
and A) impinner/condcnsatcs. Figure 6-1 shows the analytical flow scheme.
The recovered filters and probe rinses were prepared lor grauiineLric
analysis. Once part icn late wcipj.ts wero recorded, catcnes and |-robe rn.ses
were combined wii.li the appropriate .\/'.L) banole and extracted. Three sample!,
were extracted composited and .-in.-.ly/.ed from each MK5 'Irain:
• impin^cr waters and condensate,
o probe rir.sc1 (front half) .ind filtt-r,
• back half rinses and X^l) ddsorhent.
Hie latter two samples wore surtofiate-spj !;e 3,6-t ribroRophcnol, and tnen so-xlilet-extr.icrcd tor a pcijnd of 2-<-hours in
Ricthylfnc chloride.
-------
R UATHRS ACETONE FILTE».(S) HEXAME XAD SORBr.HT
r.NSATt PROBE RINSt
1
TRAIN RINSES MODULES
i
DRY, WEIGH WEIGH
1 |
I t
1
SURROGATE
SPIKE
If
*
EXTRACT WITH METHVLENE CHLORIDE (24 hrs)
DRY AND CONCENTRATE TO 1.0 ML
CC/HS ANALYSIS IN fOTAL ION MOPE
Figure 6-1. Modified Method 5 train orgnnic analysis fJow scheme.
-------
Impinp.er w.iter and condensate sn'iipl^s were extracted three times with
meihylene chloride. The extracts were then dried over sodiu.i sulfate co::ibined
with t.hc XAD/filter extract and concentrated via Kuchma Danish apparatus to
1.0 mL.
The combined extract was scanned for sumivol.it ile orndnics, us inn
capillary column gas chromatograpliy/mass spectronetry (u:/Mb) and the internal
standards. All component spectra were collected in the total ion mode. GC/'MS
instrument operating conditions are listed in Table 7-S ol thu f^iality
Assurance Project Plan. Identification ot peaks in the toral ion current
profile (TICP) was made u'sint; retention times and spectral matches to
standards. Additional compounds were identified usinj; a forward soared of tht1
N3S Library of Mass Spectral Data supplemented by nanual comparison of
component spectra with the library-derived spectra.
Chlorides—
Samples for chloride analyses were p.spared by ignition in an oxygen
atmosphere in a Parr bomb. Residues were collected and analyzed using a
Techn-lcon AntoAnalyzer II according to the protocol set forth in Method 3.J5.^
(Methods for Chemical Analysis of Water and Wastes).
GO
-------
SECTION 7
QUALITY ASSURANCE/DUALITY CONTKOL
INTRODUCTION
Quality Assurance/Quality Control (QA/QC) protocols followed in this
program were based upon routine sampling and analytical pracriccs and the
revised Quality Assurance Project Plan (QAHP) entitled Perforraa-ice Testing of
the Pyrolysis Systens, Inc. Plasma Pyrnlyais Unit, submitted for this program
on February /i, 1983. Tnis Quality Assurance suction will detail areas where
changes in laboratory and/or field procedures were made. In order to
facilitate r.jview of pertinent QC data, this section will roughly follow the
outline of the QAPP.
PROJECT DESCRIPTION
Stage II Tests
Preflare product gas was not sampled for CCl:t, 1ICI, or monitored for
velocity and temperature. The high carbon and noisture content of the gas
stream were not conducive to such Measurements. A pitct tube/pressure
transducer and thermocouple were mounted in the sample port but were removed
because hydrogen flnreb.icks created a hazard at the preflare sampling
location. The hydrogen flarebacks were essentially ignition of rlie pretlare
product ft.is from Lho flarohoad back to tKe I.D fan within the trailer,
resulting, in a minor explosion inside the fan. No further testing was
atrpmpted at this location. However, the ports were periodically used for
obtaining carbon samples, between runs.
The av.iilability of reactor ash after tost runs was limited due to the
le.ngthiness of the cool aown period and the difficulty associated in obtaining
the sample. This necessitated the removal of plasma torch, the waste i'eed
rini», coolant flsnce, and graphite core.
Stage III Tests
Two test series (2 and 3) were scheduled for the Sta^c HI level of
testing involving the destruction of PCB containing liquid waste feed. In the
effort to conplete Stage II Test Scries I an>l Stage HI Test Series 2 in
Fohrnarv 1985, Cunfiinp, >>js depleted cue to the luiigth ;if time the crow was
required to be onsite. These delays were caused hy equipment problems within
the pyrolysis system, ones which, lar?,»Iy, could not hav.'j been foreseen prior
61
-------
to actual test attempts on the d i CCure-.it waste ff.eds. Sta^o IL testing was
completed after several ntceiapts. SM?» 111 Test SLTUS 2 underwent suteral
attempts in February and March, 1985 at complet iiij; a si:ij;l(j test run but too
efforts w.-.-re unsucccssf-il after repeated pyrolysis system equipment problt.ms.
Testing was suspended until the equipment problems could he rorrct-tcd. ft >"«s
decided that a local ce->t conpany would conduct Ll-.e Stage ill Vest benes, I
testing o-i .in "on call" basis. Tins test in;; was completed in January IVbo.
CCA was contracted :o conduct the Stage 11 f Test Series 3 .°tJU endurance
tests in 1986, which were to be a ininimun of 0 nours in duration. Hie first
burn attenpl looted only 115 minutes. It was decided ac that point by NYSOuC
and PSI that shorter test burns would be necessary because it was quu-st lon.io le
as to wtiothcr thv system would stay online cor tlie duration of a full o-nour
test1. flat n.2 r than risk another aborted run, the sai-ipling time was shortened
to i-tG minutes I^ hours;. Two successful test burns were ilien cunaucced,
finishiui: Stage III Test Scries 3 arid OCn's involvement, in Hiase II
activities. Staple IV testing, as Described in :iio ^Afl', was cancelled.
PROJECT OKCANI2ATLOH AND lihai'ONSIUlMTlLS
During Chf course of this program, three major changes were mjde in oCA's
project ajid quality assurance orftaniaat ion. Mr. Haul t.xner replaced
Dr. Paul Kennclly as ProKr-jm Manager. Ms. Joan Schlosstoin replaced
Ms. Andrea Cuttnr as Analytical f)C Coordinator, and Mr. Howard Schift' replacod
Mr. Kicl.ard Graziano as Measurements \)C Coordinator.
PRCC1SION, ACCIK/\CV, CO'lI'LtTCNESS, KU'RESiKrATIVENhSS AMU COMI'AK/VBILITY
During the 'i-lu»ur I'tb -itkirancc tests, the continuous emi&bion i'ionitora
and orsat gas analyses were the only measurements in.-ide onsite. Precision
estimdtes could not be made on these measurements uith'.iny consibtf-ncy (>L.i.ausu
there were so few data points. Only two complete tc-sc runs wt-ro conductcil and
these tor only four hours. Accuracy estimates of the CbMb wero not r.aue d
lo no provision being made for audit i;as cylinders under this program. A
summary of measurement precision, accuracy, .ma completeness goals and
accomplishments is shown in Table 7-1. Tho lourly orsat data for Kuns J-2
3-3 did yield 0? mean concentrations of 14.C and lb.3 percent, respectively,
and C02 nean concentrations of 5.1 and 4.J (icrcent, respectively, btanuard
rseviations Cor hourly <>2 icadini-s were 1.04 and 0.13 ptrcent for the two
runs. C02 concentrations yielded standard deviations of U.6-'* and U.J8 lor
the two runs. The true precision of the measuremciifs cannot be estua«itcd due
to there being only four hourly neasure.aci-.ts naiie ix,r run aud no siniul taniiuus
measurements made.
Since insufficient sample volumo was avail.iulc for replicate aliquuts in
most cases, analytical precision could not be deter;n"!Cd. Analytical accur.icy
was dcten-iinod through the- analysis of EPA Environmental rionitonn}-, and
Support Laboratory ([,.slbD Quality Control Samples and the anal/sib of i.ntux
and surrogate spiked sai.iple aliquots. Kc>ults of these analyses broken down
by parameter are pi evented in Tallies 7-2 inrouj'.ii 7-o aim ^.e uiscussed oolow.
62
-------
TA3LE ;-l. SUMMARY OF CCfi PKCCISION, ACCUiiACY, AND rOMP-EPENESS
M-VTi.irr'ir.er.t
( parameter)
0
-------
TA'ilK 7-2. ANALYSIS OK A LABOKA1UKY UJl.TKil
SAMPLE FOR CIILOKIIM.S
Expeccud Kocoviirud forcenc
(JC sample (I:K/L) (i.-4j/L) recovery
WP-882-1 8.-i2 -J.UJ
6/1
-------
TABLE 7-3. ANALYSIS OF A MATRIX SPIKE INTO SCKUBbtR WA'IT.K
FOK VOLATILE OKCJASICS
Compound
1, 1-Dich loroothene
Tr ichluroochene
Chlorobor.«,,e
1o I HI; IT:
Ben:: en i:
t -jncenLr.it ion (IJ^/LJ
bxpeceeJ
50
50
50
50
50
Recovered
52
A3
•'.5
««
•'.9
I'crcent i^1. Uo ject ivc
recovor>- (Pur cone Kucovery;
lun oo-iao
86 60-140
VO ou-UO
t>8 t>0-l'»U
y8 uu-i5o
65
-------
TAJ»1,L 7-'. ANUYS1S OK A SUKKOW1E SPIKf. IHiU
SCRUUBI.K WATtK FC't VOLAITLL USliAMCS
Compound PeroiMiC Kucovury IJA ODjocLivc
Kun 2 Hun .J Avoragc (FL-rccnL
Toliitfiu.—J8 Vo yv Vfi
Broi;iotluoroboii:.;ne 121 luy 113
L,2-Uicl)loroctl!.iin!-D/* 9o L!6 ! Of>
-------
TAilLK 7-3. A.'.'AI.Y.iJb OK StM VOM! UK (.HUIAVIC tl.-VIKLX
SIUKI.U CUMiUL'i.'US (I'bliUl.r.r Ki.UA'fc.Klr.i>)
Ft I cr.ite I
flbj.ict.vvts
1,2,4-Tric.lilorobunzttic
Acen.iphchi'iu-
2,4-1'; i n 11 roc n 1 ui: n-i
N-ni.1 rosod L-u-propy Ij-nuie
'Jl
luo
1'enCcicliloropiienol
Vhanol
2-Cnlorophonol
•j-Chloro-3-iisethy IjihiM
-i-NiLroplii:nol
1UJ
74
34
91
^0-llu
HO oo
luy 7i
yj .'b
yy 7j
8U 51
75 3d
BO -to
75 40
VU J8
vu-vo
JO-l*
^U-UU
iO-110
10-UU
2»-VO
^-UU
JU-UO
10-UO
67
-------
TABLE 7-fi. ,\i.ALYSLS 0'' Si.MI VULAI ILIi UnOAi.IC aUKKUCnlo SfliC
b IN SAMl'LE A
S,.niU« 11)
St.rulibi.-r W.itur
M.'ll.uu HI. ink
Scruutur W.iiur
M.I 1 1 IK Split.:
Kun ! Scrubbur
W.i in i
Ku.; 2 SciiiMn.r
him 3 bcmlil.or
X..U/I lite: !il ink
X.«)fM,,« Spike
Kun i :'-5 lilji k
Kun I H-5
Kuii 2 M-5 bl.ink
kn:i 2 H-5
Kim 3 H-5 Bl.mV
kur. 3 11-5
,,Ob,«tU.s
Nl l rubuii/unc 2-l'luuio-
-D.J blplit-nyl
81 9'J
78 98
71 104
j9 104
6', 102
HJ 157
1 30 1 V,
128 147
129 108
133 154
13/ 169
102 150
131 147
41-120 '.4-119
Purcont k.
1
9fi
79
63
5«
50
104
93
95
82
97
08
S9
81
VJ-I2U
•i o /u i-y
J5
57
49
81
00
49
15B
142
I4d
99
162
o«
125
;*
10-110
l-i luuro-
pliC-nol
25
21
31
50
50
41
69
68
30
40
1C*
13
**
10-13d
2.4.0 fil-
plmnol
83
96
78
86
a:
85
116
H5
Ib4
til
147
103
96
IIUI1O
•il.ili I x l-.itr. vTf ..<•
-------
t^noss, defined as ths; percenia^e of all ir,o a sure meats whose results
nre juciKfd valid, was estimated to hav<* Hclucved die goal oi ^5 percent.
'.i'heri-ver possible, reference methods aiiJ st-indard 3i"iplinp, procedures wer«
used as staLed in Che 'JA ?lan to unsure coevarabi 1 ny with otiwr
representative measureir.ents made by CCA or another or^anizat ion.
SAMSUNG PROCEUUKIJS
i la , PC 131) / 1'C Ur T r a i n a
al quality control prol)Lr:.ns occurred 'Jurink> the 6a:npli::j; program
cnnducted in February l*)8b. Those problems consisted of nonisoKinntic
I'inipline, pitot tube nn-i sanplini; tr.iin leak checks, conliRurati on of ino
K'uD/PCUF train pr<>l»ij tip, and thi; .->xist«:ncc of- blocKiKc within t'lc sLJCk due
1 1) tlii- s iniiltanouns s.i.nplin>; roquiremoncs oi trie pruRraia.
S IIPII I c.inon.is S'luplinj; of a srnnll area (i.;.., a Ib-incli diaracrur btaoK)
two 3-inch di-nniter wnc^r-coc'lfld j.implinj; prubns, would load to flow
p at tli? sampling pi. me. This Mockago c.iu.scs 4 Kroaccr velocity of
the I lii«j Rq? passum the pi tot tubes and s.imple nuzzie Chan would nc -nuasurcd
uaini; smaller di.imct».r [>robu>n or a sinj-lo probe. The effect of the blockade
on tin; velocity readings bv each i IT! ivi.du.il train could not be qioerCaincd.
However, the effect or oach train would be itqunl as the uelociHiJS wore in
closi; aurntiwfnt. fat ex-rmilo, Jjvin); Run .<-<, thu velocity and flow c.it>;
nic.isurOfl bv die bcmivolnt lie tra.n was J.S43 fc/uiin and I.J04 LtJ/iaiu,
rospecc ivcl v. The saint' •nrMsuroiiiO'its taken liy Lho CCIJD/I'CUF tr^in were
3,797 fl/miji in-i 1,2"J'« ft-'/nin, rospuct ively . MIR conc.;rn« re,;.irdin^ tho
pn.i.i i!ii I ity of flow block.iKu were presented to l-i-A and New \orU SL.ito
ioc^nikii! nnrsnntiol prior, to tlio commcnrunirnl of Stu>;c 111 CesLinn. 'ihuy
concurriid tli-i1" .ilcho.ii;li flow block. i);c may UMJ.L within the S,C;..-N, the
<>i)or.it.iijiil aid citr.-j constraints of Hie program wurii sucli that 8 1 p..i L^nr-ous
q.ir:ini inj4 for scmivol jc i lo .-"iid ch lor nut u.; hi'-.id of tlic I'ClW/i'CDK probe was positioned .lp|.ro.:i::inte ly
C inchnh h.;lun.l t lie q.j-irtz waoli noazl^ dun to tlie length ol tiv int«,;rdl
quartz probe linf:r iuppii<>.d with the probe. The method call-i lor close
.lUp.pn-nt of the pitoc tius ind sinplint; nozzle. No other conf iRuration oi
the p -oiic U.TS posiible withoiit «i)cc«niivc modifications of the probn and
4arnpl*ns; hot box. This ini^ali fiiiui^nt uitiinl ly would hjv.-c<*da
tro sa'ie sjs the veloci-v at rhf* s-'iniple noazle. liowev«:r, the velocity profile
of tne stack W39 fairly flat across each line of traverse with vi-ry little
v.iriai inn belw.^n tlin points. Therefore, the ..-fleet of the Piis.ili,>iuionc on
isokinetic s.inplirn: wig not as nrp.it «•> if the velocity piofile w-is skewed ot
e r ra t i c .
;'.i i. <••- ipiini, tr.iiii .i,ij uitot L>ibe leik chocks were conducted prior to,
inJ on Ltv; c.,ntiletion liicr.(id. tloue«.;r, tlw leak chock on the
hCUO/PCiiK b.inplo trairi f<>liowinp, Ittni Ii-.'i was conducted fro™ the front-hall ol
rlie filter, becausn cl:e quartz nozzle was themal'y fhe most w.:.iiwii*'d ac two
-------
or three [joints appro* i.n »trl y J inches back from th* ?-•* b'.nd. A?.rer cooLini;
.1110 an acL-'-npt'icl leak check, this portion broke off cocpletely and fell LO the
uround. The no.:zle wan not ringed into ih" s-j-nple car.:-iin~r because; ol tnu
possible cnnt.ininal ion o£ tho lanple from carbon deposits on the ,;round. i'he
prone s>:crioii was recovered, hie train ^ak check wa^ tlion coiiJuccijd frm.i tin;
front ol the filter holder. 1C is .issiuaed that the breaita,;!.- occurred bec«u»c-
of: 1) burnt iiroiii;1! nf il.e IIIII.T occurrou WILMIII L'IK siacit c 1 rom Liu- buck,
the noz7.li' crar.k.id through fuj"! th«r.iuil shock r.:sulti i^ £ rnoiint of pji L iujl/iL.: nnlter lost in the nozzlo was
rf.'finiiiiviil to bi: nfiglmible dm; to the vory l.)w >,r,nn lo-iiliw, witijin the tlue
:;as.
The p^ii-run PCUO/I'UJK tr.iin pilot tnoo IP.I* cliccV for ili:.-» 3-^ imlevl to
ni'fit tli« leak r.-iLe r.iif!nts on the impact fiidu of the pi tot. Thy hi^h
ncn(.'< tui7ipi.-r.il ure cinsed n burnLlirou^h in tl»» probu, inc lading tin; MU.T-LZ
line- .ind pitoc tubes. It is as»ii:neJ chnc tlna burnH-.roa^h occuiroa Ou'-iu>;
tin: fin.il hfllf-hoiir of thi: run u-linn t'jmp'jr.jtijres wfre hiKhest. Th«oretical ly,
tho tent r.in should be v.,t.icd. However, the velocity hi:ad ir.iasurod Dy L>oLh
tr,u.nq uure in fairly clo-ie a:;r..'ein.!nt (U.J6 j n. II A) for the s.-aivolaci l&
tr.iin :md 0.37 in. II20 for Lhfe IIJUD/HCUF Irani ijurin^ rtun j-2). It it is.
as.timed that th« burnthro'iah occurn-d in the final minuies of tiiu test run,
the effect on ovcrnll velocity rnoasvirrimcnts would be minimal.
Thlire was n problem with nonisokin.-tic p.iaplini; of the £lu« nas during
Tast Runs 3-1 and 3-2 (si>mivolat il« train) ,ind Kuni 3-21 and J-J (I'Cliu/lViih
t r.-i-in). A L-st run is walvd and no correction or invalidation i« reij'jirutl
when rim isokinetic ratio ia bjtwciin O.'JU .i-.d '..ID. liue to Lhi- vjriuDi lily ot
I lir- wi-it^' fund and rennltint product i;ai con-'C ituonr.s, the'srack c-ji.,]>.jcatur^s
aft--r the flar» vuiied widfly. Ihe operatofs apii.'.rently were un-inle !.o Keep
up with the temoei nturi> change 1 whnn setting Lhcir iio'Mi; r/ip!,.;. The
nonnoki net i'-s of the i.wolved .s,n:n>l my runs .illect'j osi'y the colle--tion ot
p-irl iculate matter and does not .-ifl-id tli.: oolloctionot cou-pouri.la in die
v.ipor state. Vapor s-rnre nareri.nl is only affected by concenter ion
strn-iiricat ion ar. rosi the s.Tnpl in>z plane which is .il lo«;..ited by :rult ipnint
sa-iplin,: acrons thnc plane. t'arr icul-ite cono-T.cratioia and emission rates can
b value that uoiiln have been obr.iinad, hid
the saaole bean obtained i sokin.'t ical ly. This correctioa is /ive.- m
Table 7-7.
FABLK 7-7. PAKI'ICl'LATK MATTER "MlSf.I O.1 S COURK'^! 10,'.
Kun J-l Kun J-^ Kun J-J
Ib/hr concent ration
Isokiiif'ti; ratio
Ih/'hr, cot r-!*: i ••.<
IJ.U932
0.0 7dO
0.0 Job H.U52i)
i.u? I.UIM
U.f'>u7 0.'J3c>5
70
-------
Ax can b>: st-on by rhi; abovo corrvct ions, Hu: clvmne Ln emission races ifi
w:ellfcibl.> and does not Htiect tin: data appreciably.
V'JST, liCl, V\ uiU 'i|> i'i Ltn:
9a:nult! line .-".nd rf'
oE l.-ihorntory control s.naiil^s was entunbted at 108 p.-.rc.:tu. Thus.: results jr
prvsentod in Table 7-2. No pi.'cibion or accuracy j;oala uuru fistablis'.ed for
r.hloride a
Vo tatila /ind Semi volatile Ori;anicB
Qualitv contrnl pro:cdnri:a for volarU: and semivolat ile
d.:l.ennn.itions incln^d thi- .inal/aia oi mr.crvx and surroiV'te spik«d sarjple
nliiuots. K-:siilts of ch.;s« analys.is, -if.ed as -in imiicaLio.i of accuracy, .ire
lire sent *d in Tiblo.o 7-J tlircvif.h 7-6. '.^A obi-sctivcs aro prusunfid n
•»<[.»» r.tn-nt». I valuta for co-ip-iri-ion. Compl tdtmisii oajccnx-sa ol l)}~.
Otii'i.'t ions Kr-iui QA i'l?tn
In .-in rtffcrt to cur i»ronrn:.i costi, pt..>cision ol .in.iiytic.il :no.iSijr.;ia«:r>Ls
inro n;h t'o nn.-ilysii oi rcp.Lr.-'tt! saapl** nliqiioCii was 'Ot porionatci.
Rlcov.;riLi-*s ot" surio^a'O spiK-.'d cciipouno*: did not rannC i/A O&.KCLIVCI in all
cases.
SAMi'LK CUSrODV
Cai»'>l«j rn.iin-oC-Cu-Jto.lv w.i« Maintained f.iijiir;(.^ir t'v- pro v . 'ili«;,-;
proci'lnro't tr«. ii..scrib«:d \> .oclioa : ot t»u; (jujl-.'.y A--?'1 . j<-'- :'; •">"
nrepareJ TOT tiiu ;iranr «.".. It nlvislil b'j iii->Lf.-roce:luro3 .(^qcri'-cJ vo Suction l> of tli-. !M I'lan
to! 1 .<••»: d r'urinj i '. '. « irnplin r>r'j., r.trn.
/I
-------
ANAI/V TIC-XL .PROCEIJbltr S
Analytical procedures si:T.'nari7.ed in TaMe 7-2 of the QA Plan were
followed durinK this program. Several comment:* on chc QA Plan were made in
the Febr.inry 21, 1986. Ei'A ni*so from Charles Porfert, Deputy Quality Assurance
Officer, regard in?, analytical procedures (comments 1, 2, and J) . Comae nc I
requested infonn.it ion on QA objective:! for pr-.-cision, acciirjcy, and
completeness, The annlytical QC methods used are described in Section 9 of
the QA PUn; percent recovery objectives are given in Table 3-1 of Section J;
and detection Units are not required. Comment 1 re-arded certain LI1 A
analytical methods which should hi- used for analysis of sediment samples.
Comment 3 requested the use of IJI-A Method J14B for hardness. However. OUA did
not have the reagents necessary to perform this procedure and, in order not to
delay the program, Method 314 -\ was used.
DATA REDUCTION. VALIDATION, AND REPORTING
Data reduction, validation, and reporting procedures described in
Section 8 of the IJA Plan were followed durint; this program.
INTERNAL QUALITY CONTROL CIifcCKS
[ntp.rnal QC proredures described in Section 9 of the QA Fl.-jn were
followed durinR this pro^r.ir., with the exception of duplicate sample analyses
which wi.-rf not performed.
Pr.RrOllM.-\NCE AM) SYSIXK AUDITS
Analytical perfomanoe was .indited t'lroux'i the .jse of internal quality
control chocks described in Section 9 of the QA I'lan. In audition, the
1 iboratorv parcicioated in Ei>A tfatcr Pollution (WP) Siuoy ULo .md water supply
(WS) Snidy Old during tl.t- period of performance of this work. The results of
these amlyse-i, for compounds pertinent to this test Dro^r-ira, can be found in
Appendix B. i,'o systi-:a audit was conducte-i during the period of performance or
thi« wor<.
PREVENTiVE MAIN FEN \NCC
Preventive maintenance procedures dts-.cribcd in Section 11 of the QA Plan
were followed during this pi
ASSESSMENT OF PRICISION, ACCU'WCY AND COMi'Ll.TLNbbS
Analytical precision was- not reported. Accuracy assessments were ba-^ed
on tho res.ii Its of analyses of EPA Standard K.-feience Hnt^rmls and of raacnx
spik^.J s.im.)les am! reported in terns ot percent recovery which was calculneo
as shown bi.-low:
•.r.ai Recovery = lou |""1
-------
The following formula was used to estimate completeness:
C = l
whore: C = Percent completeness,
V = Number of measurements judged valid, and
T = Total number of measurements.
COaHEC! IVF. ACTION
There wen; no Corrective Action Request forms initiated in regard to this
program.
73
-------
REFERENCES
I. Quality Assurance Project Plan, "Performance Testing of the I'yrolysis
Systems, Inc. Plasma Pyrolysis Unit," Final Version, February ly£>5,
CCA/Technology Division.
2. "Presentation of.a Method for the Selection of POHCs in Accordance with
the RCKA Interim Final Rule, Incineration Standards," January 21,
Office of Solid Waste.
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