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December 1986
PILOT-SCALE INCINERATION TEST BURN OFTCDO-CONTAMINATED TRICHLOROPHENOL PRODUCTION WASTE
By
R. W. Ross. II, T. H. Backnouse.R. H. Vocque, J. W. Lee, and L. R. Waterland
Acurex CorporationEnvl ponmental SysteflB DivisionCombustion Research FacilityJefferson, Arkansas 72079
EPA Contract 68-03-3267Work Assignment 0-2
EPA Project Officer: R. A. CamesHazardous Waste Engineering Research Laboratory
Combustion Research FacilityJefferson. Arkansas 72079
For
HAZARDOUS WASTE ENGINEERING RESEARCH LABORATORYU.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI. OHIO 45268
^ \
ABSTRACT
A series of three tests directed at evaluating the incinerability of thetoluene stinbottoms waste from trichlorophenol production previouslygenerated by the Vertac Chemical Company were performed 1 n the CombustionResearch Facility (CRF) rotary kiln incineration system. The waste contained37 ppm 2,3,7,8-TCDO as its principal organic hazardous constituent (POHC).Flue gas 2»3,7,8-TCDO levels were less than detectable at all locationssampled. Corresponding incinerator destruction and removal efficiencies(DREs) were greater than 99.9999 percent. These results suggest thatIncineration of the Yertac waste 1 s ca'pable of achieving the required ORE and ^0should be considered a treatment option for this waste, r--
0000
FOREWARD
Today's rapidly developing and changing technologies and industrialproducts and practices frequently carry with them the increased generation ofsolid and hazardous wastes. These materials, if improperly "dealt with, canthreaten both public health and the environment. Abandoned waste sites andaccidental releases of toxic and hazardous substances to the environment alsohave important environmental and public health implications. The HazardousWaste Engineering Research Laboratory assists in providing an authoritativeand defensible engineering basis for assessing and solving these problems. ^Its products support the policies, programs, and regulations of theEnvironmental Protection Agency, the permitting and other responsibilities of r"'State and local governments and the needs of both large and small businesses 0In handling their wastes responsibly and economically. 0
This report win be useful to EPA's OSWER, Regional Office RCRA and °CERCLA Permit Writers, State and Local Environmental Offices. °
For further information, please contact the Alternative TechnologiesDivision of the Hazardous Waste Engineering Research Laboratory.
Thomas R. Hauser, DirectorHazardous Waste Engineering Research Laboratory
1 1 1
CONTENTS (continued)
4 Test Results . . . . . . . . . . . . . . . . . . . . . . 39
4.1 Background Burn . . . . . . . . . . . . . . . . . . 394.2 Mini burn . . . . . . . . . . . . . . . . . . . . . . 414.3 Full Burn . . . . . . . . . . . . . . . . . . . . . 454.4 Dioxin OREs . . . . . . . . . . . . . . . . . . . . 534.5 Incinerator Ash and Scrubber Slowdown Analysis ... 56
5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . 63
6 Quality Assurance/Quality Control . . . . . . . . . . . . 64CO
6.1 Measurement of Q^n . . . . . . . . . . . . . . . . . 64 ^6.2 Measurement of Qout . . . . . . . . . . . . . . . . 64
7 Health and Safety . . . . . . . . . . . . . . . . . . . . 68 000
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CONTENTS
Figures . . . . . . . . . . . . . . . . . . . . . . . . . vi'1Tables . . . . . . . . . . . . . . . . . . . . . . . . . viiiAcknowledgement . . . . . . . . . . . . . . . . . . . . . xExecutive Summary . . . . . . . . . . . . . . . . . . . . x1
1 Introduction . . . . . . . . . . . . . . . . . . . . . . 12 Facility Description. Waste Characterization and r'"
System Operation . . . . . . . . . . . . . . . . . . . . 3 00
2.1 Rotary Kiln Incineration System Description .... 3 Q2.2 Waste Characterization . . . ............ 62.3 System Operation . . . . . . . . . . . . . . . . . . 6 °
2.3.1 Incinerator . . . . . . . . . . . . . . . . . 62.3.2 Air Pollution Control System ........ 122.3.3 Residence Time Estimates . . . . . . . . . . 13
3 Sampling and Analysis Protocol . . . . . . . . . . . . . 14
3.1 Sampling Procedures . . . . . . . . . . . . . . . . 14
3.1.1 Continuous Emission Monitoring ....... 143.1.2 Continuous HC1 Monitoring .......... 203.1.3 Semlvolatile Organic Compound Measurement . . 21
3.2 Analysis Protocol . . . . . . . . . . . . . . . . . 27
3.2.1 Extraction and Analysis of Ash and AleSamples . . . . . . . . . . . . . . . . . . . 31
3.2.2 Extraction and Analyses of Water Samples * . 333.2.3 Extraction and Analysis of MM5 Incinerator
and QC Samples ............... 333.2.4 Analysis of Samples to Determine HC1
Emissions • • • • • • • • • • • • • • • • • • 363.2.5 Preparation and Analysis of Prebupn and
Feed Waste Samples ............. 363.2.6 Procedures for Physical Characterization of
Waste . . . ................. 373.2.7 Procedures for the Elemental Analysis of
Waste and Water Samples . . . . . . . . . . . 37
TABLES
Numoer Pac
1 Design Characteristics of the CRF Rotary Kiln System . . 5
2 Approximate Waste Generic Composition Based onVenae Data . . . . . . . . . . . . . . . . . . . . . . . 7
3 Waste Characterization Data . . . . . . . . . . . . . . . 7
4 Priority Pollutant Compositon of Stinbottoms Waste ... 8000
5 Incinerator System Operating Conditions ......... 10 °0
6 Calculated Average Combustion Gas Flowrates ....... 11 o
7 Continuous Emissions Monitors Available at the CRF ... 17
8 Samples Obtained During Vertac Waste Test Burns ..... 30
9 HRGC/HRMS Operating Parameters ............. 32
10 Exact Masses used for the Oetemi nation of PCDDand PCDF . . . . . . . . . . . . . . . . . . . . . . . . 34
11 Elemental Analysis Procedures Used ........... 37
12 Paniculate and 2,3,7,8-TCDO Emissions: 'BackgroundBurn of September 4, 1985 . . . . . . . . . . . . . . . . 42
13 Paniculate and 2,3,7,8-TCUO Emissions: Minlbum ofof September 9, 1985 ...... ............ 44
14 Paniculate and 2,3,7,8-TCUO Emissions: Full Burn ofSeptember 20, 1985 ................... 50
15 Paniculate and 2,3.7.8-TCDO Emissions: Full Burn ofSeptember 21, 1985 ................... 51
16 2,3.7,8-TCDO DREs: Miniburn of September 9. 1985 .... 54
17 /:.3,7,8-TCOO DREs: Full Waste Bum ofSeptember 20, 1985 ................... 55
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FIGURES
Number Page
1 Simplified rotary kiln system schematic . . . . . . . . . 4
2 Summary of the general sampling protocol . . . . . . . . 15
3 Schematic of the continuous emissions monitoring system 16for kiln and afterburner . . ..............
4 Schematic of the continuous emissions monitoring system ^for the stack . . . . . . . . . . . . . . . . . . . . . . 18 ^
05 THC monitoring system schematic . . . . . . . . . . . . . 19 Q
6 Hot zone sampling system . . . . . . . . . . . . . . . . 22 °0
7 E-duct sampling system . . . . . . . . . . . . . . . . . 24•
8 E-duct probe orientation . . . . . . . . . . . . . . . . 26
9 Stack sampling system .................. 28
10 Simultaneous dual-probe traverse employed at the stacklocation . . . . . . . . . . . . . . . . . . . . . . . . 29
11 Emission monitor data: background burn ofSeptember 4, 1985 . . .................. 40
12 Emission monitor data: mini burn of September 9. 1985 . . 43
13 Emission monitor data: full burn ofSeptember 20, 1985 . . . . . . . . . . . . . . . . . . . 46
14 Emission monitor data: full bum ofSeptember 21. 1985 ................... 47
15 THC monitor data: full burn of September 20, 1985 ... 49
16 Ambient sampler location In the Incinerator high bayarea . . . . . . . . . . . . . . . . . . . . . . . . . . 69
17 Outdoor ambient sampler locations during the Vertacwaste burns ... . . . . . . . . . . . . . . . . . . . . 71
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ACKNOWLEDGMENTS
The actual Incineration tests, results of which are reported in thisdocument, were performed by Yersar, Inc., Southern Operations, duringSeptember 1985, while under contract to EPA to operate its CombustionResearch Facility in Jefferson, Arkansas. Acurex Corporation has the currentcontract to operate the.facility, and thus the responsibility for reportingresults of these tests which, again, were performed by Versar.
TABLES (continued)
Number Page
18 2,3,7,8-TCDO DREs: Full Waste Burn ofSeptember 21 , 1985 . . . . . . . . . . . . . . . . . . . 57
19 2.3,7,8-TCDO DREs Based on E-Ouct Combined MM5Train Extracts . . . . . . . . . . . . . . . . . . . . . 57
20 Levels of PCOD and PCDF in Kiln Ash Samples . . . . . . . 59
21 Levels of PCOO and PCDF 1 n Scrubber Blowdown Samples . . 60
22 Priority Pollutant Composition of the ScrubberBtowdown Water . . . . . . . . . . . . . . . . . . . . . 61
23 Surrogate Recoveries In the Analysis of MM5 Train rn
Extracts . . . . . . . . . . . . . . . . . . . . . . . . 67 000
24 Incinerator Room Ambient A 1 r Sampling Results . . . . . . 72 Q
25 Outside Ambient Air Sampling Results . . . . . . . . . . 72 °0
1 x
• Sampling for flue gas particulate and 2,3,7,8-TCDO levels at thekiln exit, the afterburner exit, downstream of the scrubber system(the E-duct), and in the stack downstream of the system's backup airpollution control system (a caroon bed absorber fol lowed by a HEPAfi lter) using Modified Method 5 (MM5) trains. In general two trainswere simultaneously operated at the kiln exit, the afterburner exit,and the stack, and four trains were simultaneously operated at theE-duct location.
• Measuring flue gas HC1 levels at the E-duct location using acontinuous emissions analyzer
• Obtaining grab samples of the composite kiln ash, composite scrubberblowdown, and the waste feed
The analysts protocol applied to samples obtained via the aboveIncluded:
^• Analyzing the waste feed and HM5 train samples for 2,3,7,8-TCDD oo
• Analyzing the kiln ash and scrubber blowdown for 2,3,7,8-TCDO andthe po1ych1or1nated dibenzo-p-dioxins (PCDDs) and the 0
poly chlorinated d1benzofurans (PCDFs) of chlorine substitution 4 0through 8 0
• Analyzing the waste feed and the scrubber blowdown for the organicand trace element priority pollutants
All tests were performed at high excess air. flue gas 0^ was in the10 to 17 percent range tn the afterburner exit and in the 13 to 17 percentrange in the stack. CO emissions were always low, <10 ppm, as were NOxlevels, <30 ppro. Unfortunately, the continuous monitoring data are notcomplete, since problems with continuous monitor failure occurred. For themini burn test, the HC1 emission rate was 0.45 kg/hr; for the first full burntest, the HC1 emission rate was 0.25 kg/hr. Both of these are less than theCRF permit level of 0.5 kg/hr.
Paniculate levels at both the kiln and afterburner exit were quite low(in the several mg/dscm or less range) during the background bum withpropane fuel alone, as expected* Flue gas particulate levels for the testwith waste feed were highly variable and ranged from several to severalhundred ng/dsca. Due to technical and operating factors, accurateparti cut ate measurements could not be cade. Further work in this area isneeded.
Flue gas levels of 2.3,7,8-TCDO were less than method detection limitsat all locations for a11 tests. The levels at the virtual stack (thesampling point for design parameters) correspond to a DRE of greater than99.9999 percent. The virtual stack corresponds to the stack of an actualhazardous waste incinerator.
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EXECUTIVE SUMMARY
A series of Incineration experiments was performed with the VertacChemical Company's toluene still bottoms waste from trichlorophenolproduction. This waste 1 s one of the more well known of thedioxin-contaminated wastes presently 1 n existence. Samples of the wastetested In this study contained an average of 37 ppm» 2,3,7,8-TCDD (37 ug/g).The primary objective of these tests was to evaluate the incinerabnity ofthe Vertac toluene still bottoms waste by determining whether 99.9999 percent lr^destruction and removal efficiency (ORE) of the 2,3.7,8-TCDD could be coachieved, as required by current regulations. Q
The results of the tests suggest that Incineration should be considereda viable disposal method for this still bottoms waste, given that appropriate ^safeguards are employed. The data In this study confirm that Incineration 0under the conditions existing in the CRF pilot Incinerator system for thesetests is capable of achieving 99.9999 percent dioxin ORE.
The test program performed consisted a total of four trial burnsperformed in September 1985. These trial burns consisted of the following:
• A blank bum with the incinerator fired with auxiliary fuel(propane) only to establish background emission levels of pollutantsof concern
• A Binlburn of short duration (4 hours) with waste fired at nominally17 kg/hr (38 Ib/hr) to demonstrate the ability to feed andincinerate the waste and to gain experience with the samplingprotocols specified
• Two full waste test burns of nominally 10-hour duration with thewaste fired at about 10 and 18 kg/hr (22 and 39 Ib/hr) tospecifically address the test objectives
All tests were performed in the rotary kiln incineration system at theCRF with kiln temperatures maintainetf above 980°C (1800°F) and afterburnertemperatures maintained above 1110°C (2030'F). Nominal gas residence timeswere 5 to 6 sec In the kiln and about 2*5 sec in the afterburner.
The sampling protocol for the test program Included the following:
• Measuring flue gas Og, COg, CO, and MO)( levels at the afterburnerexit and 1n the stack using continuous emission analyzers
xi
The kiln ash and the scrubber blowdown water from this entire testseries was analyzed for tetra- through octa-chtoro dibenzodioxins anddibenzofurans. The kiln ash samples were devoid of PCDDs and PCDFs todetection limits ranging from 3 to 40 ppt. Scrubber blowdown samoles weredevoid of all PCDDs and PCDFs except octa-CDDs which were present at0.07 ppt. This is not surprising since octa-CDDs are relatively common inenvironnental samples.
The scrubber blowdown was also analyzed for the organic and traceelement priority pollutants. No organic priority pollutant was present inthe blowdown at levels greater than 10 ppb. In addition, none of the traceelements were present at concentrations which would cause the blowdown waterto be considered EP toxic. Based on these results, the blowdown water wouldnot be considered a hazardous waste.
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whether 99.9999 percent DRE could be achieved. However, in that the CRF IsItself a permitted hazardous waste disposal facility, the tests also had toaddress a secondary objective. These tests also represented a trial burn forthe CRF. Thus, measurements to establish whether the entire CRF incinerationsystem could achieve required DRE, particulate emissions, and HC1 emissionsand removal efficiency had to be performed. Casting these tests in the formof a research program to satisfy the primary objective, as well as aregulatory trial burn, to satisfy the CRF permit mandates, was required.
All tests were performed in the CRF rotary kiln incineration system.This system consists of a pilot-scale rotary kiln, fired afterburner, venturiscrubber/wetted elbow, and packed tower scrubber. A redundant control systemcomprised of a carbon bed and HEPA filter Is also In place. The test programperformed consisted of a total of four trial burns:
• A blank bum with the Incinerator fired with auxiliary fuel ^(propane) only to establish background emission levels of pollutantsof eoncepn . 00
0• A minlburn of snort duration (4 hours) with waste fired at nominally o
17 kg/hr (38 Ib/hr) to demonstrate the ability to feed and QIncinerate the waste and to gain experience with the samplingprotocols specified °
• Two full waste test bums of nominally 10-hour duration with thewaste fired at about 10 and 18 kg/hr (22 and 39 Ib/hr) tospecifically address the test objectives
A 1 1 tests were performed during September 1985: the blank bum onSeptember 4, the minlburn on September 9, and the full bums on September 20and 21. The tests were performed by versar, Inc.. Southern Operations, underEPA contract 68-03-3128, which expired on September 30, 1985. AcurexCorporation has since assumed CRF operation's responsibility, and has,therefore, been charged with the responsibility to reduce and summarize testresults.
Results of the tests are summarized In this report. In the following,Section 2 presents a description of the test system and summarizes itsoperation during the tests. Waste characterization data are also given.Section 3 summarizes the sampling and analysis protocols employed during thetests. Section 4 presents test results. Conclusions from the tests aresummarized in Section 5. Quality assurance/quality control (QA/QC) andhealth and safety aspects of the tests are discussed in Sections 6 and 7,respectively.
SECTION 1
INTRODUCTION
A primary function of the Environmental Protection Agency's (EPA)Combustion Research Facility (CRF) 1 s to perform Incineration testing oftroublesome hazardous wastes to support decisions regarding whetherincineration is a proper waste treatment/disposal option. One class of suchwastes is those contaminated with 2.3.7.8-tetrachlorodibenzo-p-dioxln -p.(2.3.7.8-TCDD or dioxin). w
00
Since dioxin is an extremely toxic compound, current regulations require 0that the incineration of dioxin-contanrinated wastes result in a destruction oand removal efficiency (ORE) of 99.9999 percent. For an Incinerator system Qto be permitted to dispose of dioxin-contaminated wastes it must establish,by way of a trial burn, that it is capable of achieving this level of ORE. ^However, owing to the expense of performing a trial bum, coupled with publicconcerns over performing a trial burn in which ORE could conceivably besomewhat less than 99.9999 percent, no commercial trial bums ofdioxin-contaminated wastes have yet been permitted. These concerns have beenheightened by the fact that dioxin is thought by some to be a product ofincomplete combustion (PIC) of dioxin precursor materials, so that anincineration process alight not be able to establish 99.9999 percent ORE dueto the combined emissions of undestroyed dioxin plus dioxin formed as aresult of combustion of other materials.
An example of a well-established, highly dioxin-contaminated waste isthe toluene stillbottoms from trichlorophenol production previously generatedand currently being stored, pending a decision regarding appropriatetreatment/disposal, at the Vertac Chemical Company In Jacksonville, Arkansas.The generator is currently considering onsite incineration In a mobileIncinerator system as an avenue for disposal of this waste and wishes to havea permit for a trial bum issued* The CRF was requested to perform a seriesof test bum experiments of this waste to establish whether the waste couldIndeed be considered incinerable, i.e., could 99.9999 percent DRE of dioxinbe achieved under well•control led incineration conditions. Results of theseIncineration tests would in turn be used to support any subsequent permitdecision. That is, if 99.9999 percent ORE could be established in the CRFtests, then an actual trial bum in a well-designed mobile incinerationsystem might reasonably be expected to similarly result In the required ORE.
Thus, the primary objective of the tests reported herein was to evaluatethe inclnerabnity of the Vertac toluene still bottoms waste by determining
Figure 1. Simplified rotary kiln system schematic.
0 0 0 0 8 9
SECTION 2
FACILITY DESCRIPTION, WASTE CHARACTERIZATION, AND SYSTEM OPERATION
The test program, which Is the subject of this report, was conducted inthe CRF rotary kiln incineration system. A description of this system isgiven in Section 2.1. Section 2.2 discusses waste characteristics andSection 2.3 describes the operation of the system during the testsperformed. 0
0^2.1 ROTARY KILN INCINERATION SYSTEM DESCRIPTION Q
The rotary kiln incineration system at the CRF consists of a rotary kiln °primary combustion chamber, a fired afterburner, and a primary air pollution ^control system consisting of a venturi scrubber, wetted elbow, and packed 0tower scrubber. In addition, a backup air pollution control system (APCD)consisting of a carbon-bed absorber and a HEPA filter 1 s In place. Theprimary APCD might be considered reflective of what might exist in an actualcommercial or industrial incinerator. The backup system is in place toensure organic pollutant and paniculate emissions to the atmosphere arenegligible.
A schematic of the system is given in Figure 1. Table 1 summarizes thedesign characteristics of the main elements of the system.
For these tests, waste was introduced at the feed face through the frontface lance with a Durometer type J1-10058-06D double chamber, doublediaphragm pump, while auxiliary fuel (propane) was fired through a burnerlocated at the transfer duct end of the kiln. The afterburner was also firedwith auxiliary fuel. Waste for feeding was contained in a 950L (250 gal)Tote tank placed on a Weightronic scale so that mass feedrate could bedetermined,
Combustion gases were continuously aonitored for CO, COg, 02, and NOxusing a continuous Bendix Combustion Gas Analyzer system. Readings weretaken at the afterburner exit and at the stack location downstream of the 10fan on a cycling basis. Provision also exists for extractive gas sampling Inthe kiln transfer duct. at the afterburner exit, in the duct between thepacked tower scrubber and the carbon-bed absorber (referred to as theE-duct), and at the stack downstream of the ID fan. Sampling protocols usedat each location are discussed in Section 3.1. Total hydrocarbon levels weremonitored using a Beckman heated total hydrocarbon analyzer upstream anddownstream of the carbon-bed absorber on a cyclic basis.
Normally, scrubber blowdown from the primary APCD system 1 s collected intwo permanent heat traced tanks as shown in Figure 1. However, for thesetests, scrubber blowdown was directed to two temporary storage tanks obtainedjust for these tests. The combined capacity of these tanks was noffiinally26,5iJOL (7000 g a 1 ) .
2.2 WASTE CHARACTERIZATION
Table 2 summarizes a generic characterization of the toluene sti11bottomswaste based on previous data developed by the Vertac Chemical Company. Itcan be presumed that the waste burned during these tests had similarcharacteristics. Table 3 gives results of characterization analysis performedon a sample of the waste at the CRF. Table 4 summarizes the organic prioritypollutant and EP toxicity trace metal concentrations in the waste.
2.3 SYSTEM OPERATION
2.3.1 Incinerator0^
0
The original test protocol document (1) specified performing six tests: —a miniburn conducted at waste feedrate of 17 kg/hr (38 Ib/hr), three runswith the stinbottoms waste fed at 34 kg/hr (75 Ib/hr). and background runs °with propane auxiliary fuel before and after the sti11bottoms experiments.Due to unexpected difficulties, however, a 2-week period was spent developingan acceptable feed system. Consequently, the experimental program was scaleddown to one background run, one miniburn, and two full-burn experiments. Thebackground burn took place on September 4, 1985; the mini burn on September 9;the two full bum experiments took place on September 20 and 21.
Table 5 lists the nominal Incinerator operating conditions for each ofthe tests performed. For all four, propane was fired In the kiln and theafterburner to maintain the kiln at about 1800°F and the afterburner at about2000°F. This corresponded to heat Inputs of about 260 to 350 kU (0.9 to1.2 x 106 Btu/hr) In the kiln and about 470 to 560 kU (1.6 to 1.9 x106 Btu/hr) In the afterburner for all four tests.
Combustion air was delivered to the burners by fans and the airflowrates were measured by pilot probes. These measurements were notsufficiently precise, however, because the air velocity was. low and thepressure Indicators were not ranged for the low-pressure signals. Hencethese flowrates cannot be used to compute stolchiometrles.
Two Independent methods were used to estimate combustion productflowrates, namely helium tracer and Reference Method 5 duct flowdetermination. A description of the helium tracer apparatus and Itsoperation Is provided (2). The results of these two measurements arecompared In Table 6. Theoretically, the combustion product flow should notchange downstream of the afterburner. The measured Increases In flowratesuggest that ambient air was still being drawn Into the system, which wasunder negative pressure, downstream of the afterburner. The discrepancybetween the helium tracer and Method 5 measured flowrates was in the 20 to
TABLE 1. DESIGN CHARACTERISTICS OF THE CRF ROTARY KILN SYSTEM
Character ist ics of the Kiln Main Chamber
LengthDiameterChamber volumeRotationConstructionRefractory
So lids retentiontime
Burner
Primary fuelFeed system
Temperature
2.44ni (8 ft)1.22m (4 ft)2.8a m3 (100 ft3)clockwise or counterclockwise 0.1 to 1.5 rpm0.63 cm (0.25 in.) tnick cold rolled steel12.7 cm (5 in.) thick high alumina castable
refractory, variable depth to produce afrustroconical effect for moving inerts
1 hr (at 0.5 rpm)
Iron Fireman, model C-120-G-SMG, rated at 530 kW(1.8 MMBtu/hr)PropaneLiquids: front face, water cooled lance with
positive displacement pumpSemlllqulds: front face, water cooled, lance with double
diaphragm pumpSot Ids: Metered twin auger screw feeder900°C (1650°F) maximum operating
Characteristics of the Afterburner Chamber
Length01ameterChamber volumeConstructionRefractory
Retention timeBurner
Primary fuelTemperature
3.05m (10 ft)0.91fl» (3 ft)2.096 m3 (74 ft3)0.63 en (0.25 1n.) thick cold rolled steel15.24 cm (6 In.) thick high alumina castable
refractorydepends on temperature and excess airIron Fireman, model C-120-G-SMG, rated at 530 kW(1.8 MMBtu/hr)Propanel200"C (2200'F) Baxtmum operating
Characteristics of the Air Pollution Control Syst<
System capacity
Pressure drop
Liquid flow
pH control
Inlet gas flow of 106.8 •3/mln (3773 acfm) at 1200'C(2200'F) and 101 kPa (14.7 ps1a)Venturl 7.5 kPa (30 1n. WC)Packed tower 1.0 kPa (4 In. UC)Venturl 77.2 L/roln (20.4 gpra) at 69 kPa (10 psig). tower116 L/roln (30.6 gpn) at 69 kPa (10 ps1g)Feed back control by NaOH solution addition
TABLE 4. PRIORITY POLLUTANT COMPOSITION OF STILLBOTTOMS WASTE
Concentrations Detection limitComponent (pp"i, wt) (ppm, wt)
Volatile organic priority pollutants
Methyl one chloride 2771,1-oichloroethylene NO 421.1-dichloroethane NO 42t-l,2-<l1ch1oroethy1ene MD 70Chloroform NO 841.2-dtchloroethane • MD 42l.l.l-trlchloroethane MD 42Carbon tetrachlorlde MD 70Bromochloroniethane MD 421,2-dlch'loropropylene ND 84t-l,3-d1ch1oropropy1ene MD 42Trichloroethylene MD • 42Benzene ' ND 1101.1.2-trlchlopoethane MD 42Bromofonn MD 70Tetrachloroethylene * MD 84
tetrachloroethane• Chlorobenzene . MD . 42
Toluene 159.000
Sem1 volatile organic pMoHty pollutants
l,2-<t1ch1orobenzene 2,6901,2.4-trlchlorobenzene 3»410All other base/neutral semi volatile MD 500
priority pollutants1.2-dlchlorophenol 1594-ch1oro-3-(nethy1 phenol MD 5002»4,6-tr1ch1oropheno1 ND 3002.4-dlnitrophenol MD . 3004-nltrophenol MD 5002-niethy1-4,6-<11n1tropheno1 MD 500Pentachlorophenol ND 500All other acid semi volatile priority MD 100
pollutants
^0 denotes not detected at the detection limit noted.
TABLE 2. APPROXIMATE WASTE GENERIC COMPOSITIONBASED ON VERTAC DATA
ConcentrationCompound (percent)
Methanol 1Toluene 8Dichlorobenzenes 1.5Trichlorobenzenes 1.52,4,5-tn'chloroanlsole 56Na-trichlorophenol 7D1ch1orod1methoxybenzene 162,4.5-T. Na salt 7
TABLE 3. WASTE CHARACTERIZATION DATA
Bulk density, g/ml 1.37Loss on drying, percent wt. 13.2Ash, percent wt. 5.1Heating value, HJ/kg (Btu/lb) 16.11 (6945)
TABLE 5. INCINERATOR SYSTEM OPERATING CONDITIONS
t' In OMritil
TOMB* K**t
ilO* tlu/ir)
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IMlf kHt llUO* mi/or)
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tut JII T««mr»mrt, t(•»)
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WCU —erilK
Sytt— —t*r(f)
Sr«f •I—M
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VW^I 9^11('*• MC)
»m»fl illfhif«tf«.(•»)
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>•«>•« uwt—t>«'-*lT»,r»)
>K
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;«. K/l»
>Wrt, W
itrff, t
cu tta« MC'
IMTItiM
I—U t1— MC*
M
«in» r»t», UW
— ritt, L/"1«
if »« 6.4 U (.1
Jn •r*g. «»•
y
ff^ •raw. i»«
(Sit ll
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toftr
Z<0 to 2M|0.( U 1.01
1 17 U Ml9 (O.U U 0.11)
«n u r(l.t U 1.7)
u u »(1.1 u «.«)
(.« U *.}(1.1 U I.*)
10.7 U U.t(«1 U Ml
u.» u 1.10(1.* U 2.0)
1:i*<
J
10.7(U>
O.M(I.I)
kim
W)
l—rif
30(0.»)
00
HO(17U)
».7
WO(l.M)
1120(2MO)
2.1
IS14.0)
(.2{1.1}
(.1
7»117*)
7*117?)
mi11
n«s
UHf
1(0 U(o.i u
1 1(U u
«40 U(l.t t*
10 t(2.7 U
«.* ts(U u
t.0 u
*.: u(13 U
O.X U(1.2 U
i—r»/»/Bu IU
go1.0)
• aMl
1001.7)
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t.}I.I)
(.7
10.6«)
a. io2.0)
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5010.721
17(»)
n(0.2(1
no(U2D)
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470(1.*)
11S(20M)
1.1
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7.11.*
(.2
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•
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O.*01.*
7»(1711
f'rii run!»/»/>!
1030 tc S
«*••»»
120 U UO(1.1 U 1.1)
«u a(»t» M)
o u ll«(0 t* 0.11)
iOO t* MO(1.7 to 2.6)
«.( U »(2.1 U 7.1)
1.4 U 11(0.* U l.«)
L0 U •.(
7.1 U 10.0(» U «)
0.«7 U 1.)(l.t U 1.2)
—"i)'.W
*w»»»
su(1.3)
10(221
M(0.11)
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1.7(2.1)
U
».((Mi
II(l7»)
1.0«.t)
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{M U(1.0 U
2.7 I(* U
12 U(0.9« u 0
100 U(1.7 U
(.1 t(1.1 U
«.S t(1.2 U
1.1 U LJ
7.0 U(71 U
0.11 U(l.« u
fJll 1
21/ISIt 23:
UO1.2)
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1«.U|
UO1.*)
o 21«.0)
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•rn
13!
*•«]••»«
330(I.I!
r(M)
«(0.27)
*H(1110)
*.o
120(1.1)
1 1 1 0(2030)
2.1
11(«.))
1.7(2.1)
1.2
1.1(1*1
B(D
1.M(l.t)
11(U»)
ino\0000
*tm**nM t)—« Ut— — —1—nnc 'lot ulollt— —11 m rll— l/»fr tftt— —u.
10
TABLE 4. (concluded)
Concentration3 Detection limitComponent (PP"» xt) (PP"'» wt)
Trace elements
Antimony, SbArsenic, AsBeryllium, BeCadmium, UChromium, CrCopper, CuLead, PbMercury, HgNickel, MiSelenium, SeSilver, A9Thallium, T1Zinc. Zn
NDNONONONONO4NONONONONONO
21311111111,1
10
^0 denotes not detected at the detection Unit noted.
30 percent range 1 n the E-duct. and less than 10 percent at the stack. Onepossible explanation would be that the E-duct flue gas was not fully mixed,so that the helium concentration at the probe location was lower than theactual average concentration. This would result in helium tracer flowratemeasurements being higher than those based on Method 5 velocity traverses.If this explanation were correct, then the stack gas was evidently bettermixed since better agreement between helium tracer and velocity traversemeasurements existed at this location.
The fact that Method 5 train sampling was not isokinetic (see Section 4)would not have an effect on the accuracy of a flue gas flowrate measurementbased on a pitot tube velocity traverse.
The amount of waste fed into the k 1 1 n was monitored by recording thechanges In the waste container weight reading. The feedrates fluctuated overa wide range, (see Section 4, Figures 13. 14, and 15). with mean rates of17 kg/hr (38 Ib/hr) on September 9, 10 kg/hr (22 Ib/hr) on September 20. andat 18 kg/hr (39 Ib/hr) on September 21. 1985. Waste characterization data CT\
were summarized in Section 2.2. With a measured heating value of 16.1 MJ/kg 0(6945 Btu/lb), the above feedrates corresponded to about 27 percent of"the Qkiln heat input and 10 percent of the overall fuel input on September 9. ^10 percent and 4.b percent, respectively, for September 20. and 20 percentand 8.5 percent, respectively, for September 21, 1985. as reflected in 0Table 5.
r->
During these tests, kiln and afterburner temperatures were controlled toabout 980 and lllO'C (1800 and 2030°F). respectively, by adjusting thepropane input rates. Indeed, this caused the propane heat input rates tovary. The combustion airflow methods were coupled with the -propane flowcontrol valve to maintain proper air-to-fuel ratios.
2.3.2 Air Pollution Control System
Two air pollution control subsystems were in operation during the tests.The operation of the "primary" subsystem, which Included a venturi scrubber,wetted elbow, and a packed column scrubber, was monitored. In particular,the pH of the scrubbing liquor was maintained between 8.0 and 8.6 by additionof caustic (50-percent aqueous MaOH) solution to neutralize the HC1collected.
Individual flowrates of scrubber liquor into the venturi and the packedcolumn scrubber were not monitored. Only the overall system water Inlet(makeup) and discharge (blowdown) rates were monitored. These data weresummarized 1n Table 5. Typically, 15 to 21 L/min (4.0 to 5.5 gpm) of makeupwater enters the scrubber. Approximately 8.7 L/min (2.3 gpm) of scrubberliquor blowdown was discharged.
During the test period when the still bottoms waste was fed into thek11n, this water was discharged to the onsite temporary blowdown storagetanks as noted in Section 2.1. During other times, it was discharged to thechemical sewer tine which was processed by the waste water treatment plant at
12
TABLE 6. CALCULATED AVERAGE COMBUSTION GAS FLOWKATES (dscm/rin)
Location
Ktin extt
Afterburnerexit
E-duct
Stack
Backgrour(9/4/(
Velocitytraverse*
c
c
11.8
18.3
id burn15»
llelluitracer1'
7.0
12.9
15.1
17.2
Htnibi(9/9/1
Velocitytraverse*
c
c
d
d
urnB5)
Heliumtracer1*
7.5
13.7
d
d
First ful(9/20^
Velocitytraverse*
c
c
13.1
18.3
1 1 burn'85)
Heliumtracer1*
8.2
15.1
1H.1
20.2
Second ful(y/zL
Velocityt^dve^sea
c
c
13 .4
17 .6
1 1 burn'85)
Heliumtracer'*
6.7
1 1 . 5
1 6 . 1
1 7 . 3
•Froa t«5 trains."Sea (2).ct^a velocity traverse perfomed at kiln or afterburner exits.^tto m5 trains run at E-duct or stack for •Inlburn.
0 0 0 0 9 8
SECTION 3
SAMPLING AND ANALYSIS PROTOCOL
The incinerator flue gas and residual stream sampling procedures usedand the analysis protocols employed to determine the composition of samplescollected is summarized.in this section. The sampling procedures employedare discussed in Section 3.1; Section 3.2 outlines the analytical protocolsused. 0
3.1 SAMPLING PROCEDURES0
0
The combustion gas generated during each test was monitored at various c^locations in the system for CO, COg Og, NOx. total hydrocarbon (THC). HC1, 0paniculate and trace sereivolatile organic compounds, most importantly Q2,3,7,8-TCDD, The methodologies for these efforts are discussed inSection 3.1.1 and 3.1*2 below. In addition, grab samples were obtained ofthe waste feed, the scrubber system blowdown liquid, and the ash collected inthe ash pit during the tests. Procedures for obtaining these samples arebriefly outlined in Section 3.1.2. . . .
Ambient air sampling, both in the high bay incinerator room and in theoutside vicinity of the CRF was also performed. Procedures and results ofthese efforts are described in Section 7. Figure 2 summarizes the samplinglocations and types of samples obtained for this series of experiments.
3.1.1 Continuous Emission Monitoring
Online Instrumentation was used for monitoring CO, CO?, Og. NOx, andTHC. Table 7 lists the Instruments used to monitor each of these and theirprinciple of operation.
Combustion gas can be monitored on a time-sharing basis at the kilntransfer duct and at the afterburner exit. However, for these tests, alldata were taken at the afterburner exit. The monitoring system serving thesetwo locations 1s shown schematically In Figure 3. This system consists of:
66-011 (26-1n.) Hastenoy C-276 probes12ra (40 ft) of 1/4-1n. heat-traced Teflon line .Liquid water bubbler for moisture and paniculate removalAir actuated valves that select the desired sampling location12ni (40 ft) of 1/4-1 n. polyethylene transfer line
14
the Pine Bluff Arsenal. Approximately 40 to 50 percent of the makeup waterwas evaporated and ended up as water vapor vented with the combustion gasproducts out the stack.
The pressure drop across the venturi scrubber was about 8.5 kPa (34 in.W C ) with variations of about 1 kPa (4 in. W C ) . The packed column pressuredrop ranged from 0.5 to 1.2 kPa (2 to 5 in. W C ) . The draft at the kiln ranat about -25 Pa (-0.1 in. WC) and hence would not leak any combustion gases.The large pressure drops across the venturi and the packed column scrubberswere supported by the large induced draft fan which pulled up to 11-kPa(45-in. WC) vacuum.
2.3.3 Residence Time Estimates
In addition to Incineration temperature, residence time 1 s an Importantparameter In the effectiveness of an Incineration system In destroyinghazardous organic compounds. For this test program, residence times were _calculated based on volumetric flowrate measurements using the helium tracersystem and the assumption that the kiln and afterburner chamber temperatures °were Isothermal and equal to the single point measurement. I.e., nominally K-980°C (ISOO^F) at kiln and 1110°C (2030°F) at afterburner. It Is recognized othat the resultant residence times will not be precise, but they w i 1 1 serve ^as approximate Indicators.
0The calculated residence time in the kiln main chamber was 5.7 sec for
the blank bum, 5.3 sec for the mini burn, and 4.9 and 6.0 sec for the twostnibottonis waste full burns. Residence times in the afterburner were 2.1,1.9, 1.8, and 2.3 sec for the respective tests.
REFERENCES
1. "Protocol for an Incineration Study of 2,4.5-T StUlbottoms with TCUOContamination." prepared by Yersar, Inc.. Southern Operations, fopEPA/HWERL. Combustion Research Facility. July 1985.
2. Games, R. A., and F. C. Whitmore, "Characterization of the Rotary KilnIncinerator System at the USEPA Combustion Research Facility (CRF),"Hazardous Waste. Vol. 1. No. 2. p. 22b (1984).
13
L
Kiln
1^ ^7 <Afterburner
1s ^
1
««
Vent lo kiln (?«• (.10 f t ) of 1 /2 In. copper tuliinq)
CM (Z6ttostelli
pri
•^
12- (40 fthe«t t
n.) J/U In. Icf>V C-Z76•be
1
» 1 /4 In. /
I'o11."'1 U-*M••• /I01* wier / Airbobt»»e7\ «•(
W»1
^
<
^•rM- Pure" |rfrtT —*'
12» (40 rt) 1/4 In.polyethylene line
^ 1
——L—Q-A^-A
<1 s,,. /slalnles* /r
itee) —nliold
dH
H
EH-onltor He
0.
-oi.lliir
NO(ton 1(or
^}«1lor
—»——•
r
lo peeked lowerwet tcrubber
Figure 3. Schematic of the continuous emissions monitoring system forkiln and afterburner.
0 0 0 1 0 1
•
Parameter p
COg
02
CO
NOx
HC1
THC
SenivolatUe 3.4,6,8 Modified Method 5 10 hurganlcs (7 dIncluding (2502.3.7.8-TCDD
Haste
K 1 1 n ash 2 Grab
Scrubber 5 Grabblowdown
! -U»T
1 1 2 1
3
3
3
3,4,8 Chemit luminescence Continuous
6 Colorimetric Continuous
6,7 Flame 1on1zat1on Continuous^ —detector
1
ii
Testoints Methodology
,4,8 MDIR
,4,8 Zirconiumsensor
,4,8 NDIR Continuous
Grab
..——
Jli«i
•It—
"•"
'<C1—
'-7"in
oxide
T " *" 7filur
it) in
Sample No. ofduration samples
Continuous
Continuous
8 caaftebum
8 caafteburn
'<lur
ours 2 at test pt 3sere 2 at test pt 4dscf)) 4 at test pt 6
2 at test pt 8
mposites 8r entireseries
mposltes 8r entireseries
-\^)——
'
3
55
n
<M0<>—
0
00
SThe two test points were monitored by one Instrument on a 5-fflln. time-sharingbasis.
Figure 2. Summary of the general sampling protocol.
15
CO CO,
Pen—-Puredrier
Monitor Honllor
61 f (74 I n . ) 1/1 In.stalnleii tteel profce
IbDi (50 1 1 ) 1/4 III.heat-traced tefloii 12« (40 ft) 1/4 In
•polyethylene (If
91 ۥ (16polyethyh
(«.l }/• In.Inr
Monitor
NO
Monitor
Utter droplelre-ovl visel
liquid wl«rbubbler
Pi—p and*t*lnle*tsteel deliverysysler
Flycre 4. Schemattc of the continuous emissions monltortnJsystem for the stack.
° 0 0 1 0 3
TABLE 7. CONTINUOUS EMISSIONS MONITORS AVAILABLE AT THE CRF
Parameter
02
CO
C02
NOx
THC
Instrummanufacand mod
BendixModel
BendixModel
Bend1xModel
BendixModel
BeckmaModel
entturerel no.
304
8903
8903
8101C
n402
Method ofdetection
Zirconium oxide
NDIR
NDIR
Chemi1uminescence
Flame ionization
Range
0 to 25 percent
0 to 100 ppm0 to 1000 ppm
0 to 10 percent
0 to 150 ppm
0 to 50 ppn
• A Perma-pure* drier, for additional moisture removal (conditionsCO/COz sample stream only)
• Sample pump and stainless-steel manifold delivery system• Analyzers for C0» COg, Qg, and NOx
Each of these Instruments vents the sample back to the kiln via a 1/2-ln.copper line.
The combustion gas leaving the stack can also be monitored on atime-shared basis using the same bank of monitors noted above. The stack gassampling system is illustrated in Figure 4 and consists of:
61-cm (24-1n.) 3/8-1n. stainless-steel probe91-cm (36 In.) of 1/4-1 n. polyethylene transfer lineWater droplet removal vessel15m (50 ft) of 1/4-ln. heat-traced Teflon transfer lineLiquid water bubbler for additional water removal12m (40 ft) of 1/4-ln. polyethylene transfer lineFurther gas conditioning and analyzers as noted above
A separate continuous monitoring system shown schematically in Figure 5uses a THC analyzer to provide Information on the efficiency of thecarbon-bed absorber. This system alternately measures the THC concentrationin the combustion gas entering the bed and leaving the bed. Each of thesetwo sample points Is served by:
17
30-cm (12-in.) 3/8-in. stainless-steel probe46-cm (18-in.) of l/4-in. Teflon transfer lineGlass water droplet removal vessel6ni (20 ft) of 1/4-1n. heat-traced Teflon lineA timer-control led solenoid valve (5-niin. cycle)
The two sample lines converge to 46-cm (18-in.) of l/4-in. Teflontransfer line. This in turn is converted to 46-cm (18-in.) of l/4-in.stainless-steel transfer line that enters the Beckman 402 THC analyzer.
3.1.2 Continuous HC1 Monitoring
In addition to the traditional combustion gas continuous analyzer systemdescribed above, HC1 emissions were continuously measured in the flue gas atthe E-duct location during the mini bum test on September 9 and the full burntest on September 20. These measurements were performed using a CEA modelTGM 555 color! metric analyzer placed at the E-duct location. ^
The TGM 555 monitor is an automated wet-chemical colorimetric analyzer. 0
In principle, hydrogen chloride liberates thiocyanate ion in mercuric ^~thiocyanate solution by the formation of soluble mercuric chloride. In the opresence of ferric 1on» highly colored ferric thiocyanate is produced. The QIntensity of the color formed is measured at 480 nm and is proportional tothe concentration of hydrogen chloride present. The Instrument has a digital °meter that reads out as a percent of full scale, and is capable of exceeding100 percent. For example, if the unit Is calibrated for 0-2 ppm full scalefor a chemistry that is linear up to 3 ppm, a reading of 063 on the meterwould indicate 1.26 ppm, and 112 would be 2.24 ppro.
The TGM 555 measured the concentration of hydrogen chloride in theE-duct gas by monitoring the amount of color change produced in theanalyzer's working color reagent system. Flue gas was continuously drawnInto the instrument via an Internal vacuum pump through an appropriate Teflonfitting, and then through a vertical glass gas/liquid contact absorber coil.Reagent absorbing solution was drawn from Its reservoir by the liquid pumpand was transported concurrently downward with the air stream through thecoil to absorb the gas parameter to be measured. The absorbing solutionreacts with the effluent and produces a color change. Unreacted reagent ispumped through the reference cell of the dual-beam colorimeter of theTGM 555. The colored reaction product flows through the sample cell. Thecolorimeter measures electronically the difference in light absorption of thereagent before and after the reaction with the hydrogen chloride.Transmission of light through the flow cell 1 s measured by a matched set ofphotodetectors at a particular wavelength.
The electrical signal generated 1n the colorimeter is amplified and fedto a digital display where it Is read out as a percentage of full scale. Themeasurement range of the Instrument can be adjusted to be 0 to 1.0 ppm to0 to 50 pom or even higher with the addition of a sample splitter.
20
CartHittlon product*fro* p«ckt4
tONT scrubber
CTbon fllfr
1/4 (•. • II In{«()*• 1(—
3/11 III. 11 12 IM.st«liiles» ifl
prote*
1/4 (n. K 20 ftbe*t-lr«ced
IcflOM
M«lT dropletrwo««l wsri
(9l*»<)
•eckiun 40211X «n*lyier
SteckID fn
Figure S. THC iiwnttortng system schematic.
0 0 0 1 0 6
61 CM (24 III.) 1/4 IN.Maiflloy C-Z7C
116 SfliilRfile«l flltinq
61 CM (24 In.) 1/4 III.Hasflloy C-Z/6
Vent lo_Uln
Saith-GireenburqiHplnqer Mllh ill If gel
Flyure 6. (lot zone sampling system.
0 0 0 1 0 7
3.1.3 Semi volatile Organic Compound Measurement
Semivolatile organic compound emissions, most Importantly 2,3,7,8-TCDO,the POHC for these tests, were measured at four locations in the system asshown In Figure 2. The sampling methodology followed that outlined in theASME MM5 protocol (3) with some modifications necessitated by the conditionspresented by the environments of the different sampling locations.
Sampling conducted at the kiln transfer duct and afterburner exit ductutilized a combination condenser/resin capsule unit. Conditions at theselocations were unsuitable for isokinetic sampling so strict MM5 proceduresand equipment were not employed. The sampling train shown in Figure 6 wasused to sample at this location. This train consisted of:
61-cm (24-1 n.) 1/4-1 n. Hastelloy C-276 probeAn unneated 46-cm (18-ln.) 1/4-1n. Hastenoy C-276 transfer line y^Inline, type-<J thermocoupleAn unneated 15-cm (6-1n.) 3/8-1n. Teflon transfer line 0
Glass fiber f liter assembly •'—Condenser/resin capsule assembly containing 30g of XAD-2 resin oA second type-J thermocouple • QEmpty SmIth-Greenberg ImplngepSmith-Greenberg impinger containing 750g of silica get 0
In assembling the train. Teflon sleeves, rather than grease, were usedIn the joints located upstream of the XAD-2 resin.
Though no additional heat was added to the transfer line and filterassembly, the temperature of the sample gas measured just ahead of the filterwas usually 95° to l20°C (20U° to 250°F) during sampling. In the rangespecified in Reference to Method 5.
At the beginning of each sampling period, flowrates through the resinaveraged 20 to 25 L/re1n. During the course of a 10-hour sampling period,however. Increased paniculate loading on the filter would typically cause areduced flow to the 5- to 10-L/min range.
For each test performed (blank burn, miniburn, and two full burns)two sampling trains were run simultaneously at both the kiln transfer ductand the afterburner exit. Plans for each test were to operate all trains fora 10-hour period during which nominally 7 dscm (250 dscf) of combustion gaswould have been collected. However, during most tests, operational problemsoften developed which resulted In the collection of smaller volumes at somelocations.
When sampling was complete* the train was leak tested, disconnected fromthe probe/transfer line assembly, and transported to the laboratory forsample recovery. The probe and transfer line were sealed at each end andtransported to the laboratory where they were rinsed three tiroes with 500 nil
21
Figure 7. E-duct sampling system.
0 0 0 1 0 9
of a 1 : 1 mixture of methano! and methylene chloride. Probe rinses becameanother sample for analysis.
Sampling for semi volatile orgamcs also took place in the horizontalduct between the packed tower scrubber and the carbon-bed absorber, referredto herein as the E-duct. The carbon bed al lows for operation of theincinerator under experimental, noncompilance conditions by providingpurification of flue gas before it is emitted to the atmosphere. For theseincineration experiments, the E-duct was the sample point of choice becauseit is at this point that the CRF's flue gas mimics a typical incinerator'sstack emissions.
The sampling system used consisted of four identical trains, eachconnected to its own fixed probe/pi tot tube assembly. The train/probeassemblies are described in detail in the following and Illustrated inFigure 7. Q
• Probe/pilot tube assembly: A 1/2-1 n. 00 316 stainless probe nozzle '~was connected to a 3/8-1 n. 00 glass probe with a 5/8-1 n. to 3/8-1 n. T"316 stainless-steel reducing union tube fitting and Teflon ferrules. 0The glass probe was sheathed with a 1/2-1n. 00 stainless-steel tube Qwhich was butt welded to the nut of the 3/8-1n. side of the reducing —^union (as Is done with most commercially available sampling probes).A second 3/8-1n. nut was welded to the other end of the 3/8-1n.probe sheath and Teflon ferrules were used to seal this end of theglass probe to the sample line. A type "S". pilot tube was-mountedalong the side of the -above-mentioned probed sheath, as required byMethod 2. The entire assembly was sheathed by a 1-1n. 00 3/8-1n.stainless-steel tube which was sealed In the duct port with a tubefitting and teflon ferrule. To prevent ambient a1r from leakingInto the duct through the sheath, a sealant was placed Inside thesheath In a 6-1n. plug that was located 7.5 to 10 en (3 to 4 in.)back from that end of the sheath which Is exposed to the stack gas.
• Sample line: A 6l-c» (24-ln.) length of 3/8-ln. OD Teflon line wasattached to the probe assembly with a 316 stainless-steel tubefitting
• Condenser/resin cartridge assembly: The Teflon sample line wasconnected to a 28/15 glass socket with a 316 stainless-steel tubefitting and teflon ferrules. This socket was sealed to the Inlet ofthe condenser/resin cartridge assembly, with the use of a Teflonsleeve. All glass to glass Joints located upstream of the resincapsule were sealed with the use of Teflon sleeves, rather thangrease.
• Moisture removal components: The outlet of the assembly sat on topof a 41 condensate trap, connected to an impinger containing silicagel via a glass elbow
23
Figure B. E-duct probe orientation.
. 0 0 0 1 1 i
This train was used for the blank burn conducted on September 4, during.which no waste was Introduced to the incinerator. During the waste feed fullburn on September 20 a heated filter was added to the train. The 61-cm(24-in.) 3/8-in. Teflon line was connected to the inlet of the heated filterwith the use of a glass socket adapter and a stainless-steel tube fitting.The outlet of the filter connected to the condenser/resin cartridge assemblyIn the sane manner. During the September 21 full burn, an unheated filterwas used, plumbed in the train as described above.
As was noted above the "8 and 2 diameter" requirement of Method 2necessitates an Inordinate length of duct if four simultaneous samplers areto be used at four separate sampling locations. However, a valid isokineticsample can be obtained if the four samplers are served by separate probes,each sampling in the same vertical plane at one-half the required number ofpoints on the two perpendicular traverse lines. Because all probes sampledfrom the same vertical plane, only a 3,7-w (12-ft) length of duct wasrequired. Figure 8 shows a cross section of the E-duct, along with thelocation of the four probes.
CM
For a 35-cm (14-ln.) diameter duct. Method 1 requires four points on ^each perpendicular traverse line. When sampling began, each of the probeswere positioned at the outer-most points of the two traverse lines. With the °probes In this position, flue gas was sampled at half of the required eight 0traverse points. Later In the experiment, each of the four probes weresimultaneously moved inward to the next traverse point. Thus the duct wasbeing sampled at the remaining four points. Because all four pitot/probeassemblies were located in the same vertical plane, they did not affect eachother. A thermocouple probe was used to measure the stack gas temperature atfour points on a horizontal traverse line located 61 en (2 ft) upstream ofthe sample point.
To detect leaks, which may have resulted from moving the probes, heliumtracer was injected Into the Incinerator system for the duration of theexperiment. After the probes were moved and re-sealed In the duct ports.Mylar gas sample bags were connected to each of the sailer's pump exhaust.Simultaneously, a 5-L/min sample of flue gas was extracted from the duct andconveyed to a thermal conductivity gas chromatograph. By comparing the peakheight of this sample to that generated by a manual Injection of sample fromthe Mylar bag, any ambient air leak Into the duct was evident.
At the conclusion of each experiment, the sample trains weredisconnected from the transfer lines, and the probe, transfer lines, filters,and trains were sealed and transferred to the laboratory where all traincomponents located upstream from the resin were rinsed as described earlier.The filter and resin were extracted and these extracts, along with theabove-mentioned rinses were cleaned and reduced to 1 ml. Thus reduced, theextracts of all four samples were analyzed by GC/MS to quantitate the DRE for2.3.7.8-TCDO.
25
U«lnl*lt tlwl (Illliq
V^— Clltl •diyttr
1«(1— <lr««*
1/1 <•. ir((•(ill*** «(—1——t|« l.f- 14 «) I/? In.
•(•**• I liw4 pcbe
*• (r ft) i/? «ii.ylrftkyi— II—* ~V(
Ftyure 9. Stack sampllni) system.
0 0 0 1 1 3
Trace organics were measured in the stack emissions with the use of twostandard MM5 trains as shown in Figure 9; each of these consisted of:
• Stainless-steel probe nozzle
• Glass-lined prooe/pitot tube assembly
• Heated filter
• 3/8-in. 00 Teflon transfer line (unheated) which connected to thefilter with a 28/15 glass socket. The socket was connected to theTeflon line with a 3/8-1n. stainless-steel tube fitting.
• Condenser/resin cartridge assembly, which was connected to theTeflon transfer line with a 28/15 socket and tube fitting asdescribed above. At the outlet of the resin cartridge, a ';;d-1 1 quid-in-glass thermometer was sealed in the assembly with a —.threaded adapter. This provided temperature measurement of the _cooled sample. '~
0• The condenser/resin capsule assembly connects directly to a 4L 0
condensate catch, with the use of a 28/15 ball/socket combination o
• Sroith-Greenburg Implnger, containing silica gel. This Impingerconnected to the condensate trap with the standard 28/15 ball socket"U" connector.
As was noted In the discussion of the other sample trains. Teflonsleeves, rather than grease. Mere used in those joints located upstream fromthe resin capsule.
The two trains were operated simultaneously In the stack downstream ofthe Indirect draft fan, each train traversing only one of the traverse linesIn a manner such that one probe did not Interfere with the other. This wasaccomplished by starting the sample with the probe of one train positioned atthe traverse point furthest from the duct port, while the other probe startedIts traverse at the point closest to the duct port as Illustrated InFigure 10. The partlculate collected In the front half of each train wascombined to determine the partlculate emission rate. The resin from eachsampler was extracted and these extracts combined and analyzed by SC/MS todetermine 2,3,7,8-TCOO levels In the stack emissions.
3.2 ANALYSIS PROTOCOL
Table 8 summarizes the total number of samples obtained during each ofthe tests performed In this program. A total of 80 samples was obtained; 70were analyzed and 10 archived. There are seven different sample typesrepresented in this enumeration.
A variety of anaytical procedures was used to determine parameters ofInterest in samples selected from Table 8. For example, ambient air, kiln
27
TABLE 8. SAMPLES OBTAINED DURING VERTAC WASTE TEST BURNS
Sample type
Waste samples:
• Preburn samples• Incinerator feed
samples
MM5 Incineratorsamples:
• Kiln transfer duct• Afterburner duct• E-duct• Stack
Scrubber blowdown samples
A 1 r samples (see Section 7)
HC1 samples:
• Continuous analyzer(CEA)
• MM5 Impinaeps
Kiln bottom ash
Q.C. samples:
• Field spike (MM5)• Field blank (MM5)
Sample dates
Sample9/4/85 9/9/85 9/20/85 9/21/85 Other total
6 62 2
in2 2 2 2 8 ^2 2 2 2 84 . 4 4 122 2 2 • 6 °
08 8 o
. 1 6 2 9
1 1 2
1 4 5
8 8
•
1 1 1 31 1 1 3
Total 8Q
30
First position Second position
Third position Fourth position
Figure 10. Simultaneous dual-probe traverse employed at the stack location.
29
TABLE 9 . HRGC/HRMS OPERATING PARAMETERS
Mass resolution
Electron energy
Accelerating voltage
Source temperature
Preamplifier gain
Electron multiplier gain
Transfer line temperature
Column
Injector temperature
Column temperature — Initial (3 min)
Column temperature — program
Column temperature — final
Carrier gas
Flow velocity
Injection mode
Injection volume
9,000 to 12,000 (M/AH, 10-percentvalley definiton)
70 eV
6,000 volts
200°C
107 volts/an?
~106
ZSO'C
OB-5 30m or CP S11-88 50ni
300aC
160°C
30aC/m1n
250'C (CP S11-88)
290'C (DB-5)
Helium
"•25 cm/sec
Splitless
2 u1
32
bottom ash, and scrubber blowdown liquid were analyzed by high-resolution gaschromatography/high-resolution mass spectrometry (HRGC/HRMS) forpolychlorinated dibenzofurans (PCDF) and polychlorinated dibenzo-p-dioxins(PCDD) of chlorine substitution 4 through 8. Flue gas samples were analyzedby HRGC/HRMS for 2,3,7,8-TCDD only. Waste samples were analyzed by bombcalorimetry for higher heating value. The analytical methodologies used aresummarized in detail in the following subsections.
3.2.1. Extract ion and Ana lys i s of Ash and A i r Samples
Each of these samples was spiked with Isotopically labeled internalstandards and Soxhiet extracted for approximately 18 hours using benzene.The ash samples were spiked with 25 ng each of 2,3,7,8-tetrachlorodibenzo-p-dioxin-13Ci2 (2.3,7.8-TCOO-13Ci2), 2.3.7.8-tetrach1orod1benzofuran-l3Ci2(2.3.7.8-TCOF-13Ci2). and octachlorodibenzo-p-dloxin-^c^ (OCOD-^C^).while the air samples, which had beerr spiked with 2.5 ng each of 002.3,7.8-TCUD-^3q2 and 2,3.7.8-TCDF-13Ci2 before sampling, were spiked only .-with 5 ng of OCDO-13^. ,-
The benzene extracts were concentrated to approximately 4 ml using °three-stage Snyder columns, and transferred to multilayered columns 0containing activated silica gel, 44-percent concentrated sulfuric acid on 0silica gel, and 33-percent 1M sodium hydroxide on silica gel. The columnswere rinsed with 70 ml of hexane and the entire elutates were collected. Thepurpose of these columns was to remove acidic and basic compounds from theextracts as well as oxidizable materials.
The benzene/hexane elutates were concentrated using a gentle stream ofnitrogen gas and solvent exchanged into hexane. The hexane solutions wereehroroatographed through columns containing approximately 1 gra of activatedbasic alumina using methylene chloride (97:3, v/v) , and hexane/methylenechloride elutates were collected, concentrated to near dryness, and dissolved1 n 20 u1 of an absolute recovery standard containing 1.2,3.4-TCDO-13c^2. Allsolutions were stored at 0°C and protected from light until analyzed.
The extracts were analyzed for PCDD/PCOF using capillary columnHRGC/HRMS. The HRGC/HRMS consisted of a Carlo Erba Model 4160 SC withModel 7070 mass spectrometer. The primary chromatographic column was a 30-<n08-5 fused silica column using helium carrier gas at a f1o» velocity of25 cm/sec. The mass spectrometer was operated In the electron Impact (El)ionlzation mode at a mass resolution of 9,000 to 12,000 (M/aM, 10-percentvalley definition). The operating parameters of the HRGC/HRMS are summarizedIn Table 9. The primary analyses, to determine the total level of eachPCDO/PCDF class, were carried out using two separate HRGC/HRMS runs. Thiswas necessary due to chromatographic overlap of adjacent Isomer classes andhardware limitations to the number of masses that could be sequentiallymonitored. The first run provided data for the PCOD and PCDF Isomers havingan odd number of chlorine substltuents, while the second run determined thelevels of the isomers containing an even number of chlorines. Although theDB-5 capillary column is excellent for PCDO/PCDF Isomer class determinations,It does not provide the Isomer specificity of the more polar phase columns.
31
TABLE 10. EXACT MASSES USED FOR THE DETERMINATION OF PCUD AND PCDF
TheoreticalAccurate mass isotope r a t i o
Compounds Mass 1 Mass 2 Mass I/Mass 2
Tetrachlorodlbenzo-p-dioxins 319.8965 321.8936 0.77Tetrachlorodibenzofurans 303.9016 305.8987 0.77Hexachlorodiphenyl ethers 375.8364 377.8334 1.23
Pentachlorodlbenzo-p-dioxins 355.8546 357.8517 1.54Pentachlorodlbenzofurans 339.8597 341.8567 1.54Heptachlorodlphenyl ethers 409.7975 411.7944 1.03
Hexachlorodlbenzo-p-d-loxins 389.&156 391.8127 1.23Hexachlorodlbenzofurans 373.8207 375.8178 1.23Octachlorodi'phenyl ethers 433.7584 445.7555 0.88
Heptach1orod1benzo-p-d1 ox-Ins 423.7766 425.7737 1.03Heptachlorodlbenzofurans 407.7817 409.7737 1.03Nonachlorodlphenyl ethers 477.7194 479.7165 0.77
Octach1orod1benzo-p-d1ox1n 457.7377 459.7347 0.88Octachlorodlbenzofuran 441.7428 443.7398 0.88Oecachlorodlphenyl ethers 551.6805 513.6775 0.69
34
Since 2,3,7,8-TCDD and 2.3.7,8-TCDF are the most toxic PCOD/PCDF isomers, allsamples that were found to contain TCDD or TCDF using the DB-5 column werereanalyzed using a 50-m CP Sil-88 fused si l ica capillary column whichresolves 2,3,7,8-TCDO fropi the other 21 TCDO isomers. Whi le this column doesnot provide complete separation of 2,3,7,8-TCDF from the other 37 TCDFisomers, the level of confidence is far greater than with the DB-5 column andis considered to be state of the art. All HRGC/HRMS data were acquired bymultiple-ion-detection using a VG Model 2035 Data System. The exact massesthat were monitored are shown in Table 10.
3.2.2 Extraction and Analyses of Hater Samples
Each water sample was filtered. The liquid portion of each sample wasspiked with 5 ng of 2,3.7.8-TCDO-37C^4 and 20 ng of hepta-COO-^Cl 7 andextracted with methylene- chloride. The solid paniculate matter samples werespiked with 5 ng of Z.aJ.S-TCOO-13^. 2 ng of nexa-CDO-13^. and 20 ng ofocta-CDO-13^ and Soxhiet extracted with benzene for 16 hours.
Extracts of the liquid and partlculate samples were subjected toseparate cleanup procedures using micro alumina and carbon columns.. Aliquotsof each of the two extracts representing an original water sample werecoinjected Into a 30ni SE-54 fused silica capillary column for HRGC/HRMSanalysis.
Similar extracts were also analyzed for the semi volatile organicpriority pollutants by Method 8270. .
Whole water samples were analyzed for the halogenated volatile organicpriority pollutants by purge and trap 6C/e1ectron capture detector (ECD) byMethod 8010.
3.2.3 Extraction and Analysis of MM5 Incinerator and QC Samples
Sample harvesting and processing from MM5 trains were performed in theCRF laboratory by the chief chemist, his assistant and two technicians.Several practices were adopted to minimize cross-contamination among trains.These included:
• All samples from one bum must have cleared the laboratory beforeanother bum can be Initiated
• A11 the glassware used to assemble a train, and to process thesample extract harvested from It, constituted a unique set and werealways used together to take and harvest samples from the sameIncinerator location
• A given train was processed from receipt In the laboratory tofinished extract by one and only one worker
Each MM5 sample consisted of impinger condensats. probe washes, glass fiberfliter catch, and XAD-2 sorbent resin.
33
• Inject a 2-u1 aliquot of the extract into the GC, operated underacceptable calibration procedures to produce acceptable results withthe performance check solution
• Acquire mass spectral data for the following selected characteristicions: M/Z 257. 320, and 322 for unlabeled 2,3,7,8-TC30; M/Z 328 for2.3,7,8-TCOD-37ci4; and M/Z 332 and 334 for 2,3,7,8-TCDD-13Ci2. Usethe same data acquisition time and MS operating conditions used todetermine response factors.
As will be noted In Section 4, the results of these individual MM5 trainanalyses were that 2,3,7,8-TCDD was not detected in any individual MM5 train.However, the detection limits of the procedure used were not low enough toallow quantitating 99.9999 percent 2.3.7.8-TCDD ORE.
In an attenpt to improve detection limits on a ng/dscm basis, theextracts from the four MM5 trains operated simulatneously at the E-ductlocation were combined subsequent to the individual extract analyses and 'these pooled extracts analyzed for 2,3,7,8-TCOO. In these analyses, (performed at the CRF, the pooled extracts were again subjected to the above T-extract cleanup procedures, concentrated to 50 u1, then analyzed by oHRGC/LRMS for 2.3.7.8-TCDO In accordance with Method 8280 (revision dated ^May 12, 1986) procedures. The choices for GC capillary column (60m, DB-5),GC temperature program, and selective Ion monitoring schedule were taken from 0
(4).
3.2.4 Analysis of Samples to Determine HC1 Emissions
Monitoring of flue gas for hydrogen chloride was performed using twomethods: the continuous HC1 monitor discussed in Section 3.1, and byanalysis of the MM5 train inplnger solutions for collected chlorides asoutlined In the following.
Altquots (0.5 n1) of the MM5 1«p1nger condensate were analyzed with anOrion Research Model SOU digital lonalyzer. Chloride Ion measurements of5-<nl aliquots of the MM5 condensate were made with a specific Ion electrodeand digital pH meter with expanded millivolt scale. A I-IBV change Inpotential corresponded to a 4-percent change in concentration when thisnonovalent Ion was being measured.
3.2.5 Preparation and Analysis of Prebum and Feed Haste Samples
For the waste samples, 1-g allquots were weighted out and spiked with100 ng of 1.2.3.4-TCDO-l3Ci2. 50 ng of 2,3.7.8-TCOO-13Ci2. and 10 ng of2,3,7.8-TCDO-37ci4. Six «T of methane! and 4 m1 of benzene were added toeach aliquot. Then 200 u1 of the aliquot was diluted to 1 n1 with hexane.
Standard extract cleanup procedures Included multilayer acid/base silicage1 (Davison Type 60, 70-230 mesh) column and acidic alumina (Fisheractivate 1, 80-200 mesh) gravity column chroroatography and Carbopack C
36
(Supeico 8Q-10U mesh) column.concentrated to 50 u 1 .
After the sample cleanup, the aliquots were
The samples were analyzed for 2,3,7,8-TCDD on a Finnigan 4000 HRGC/LRMS.The colunn used was a SP-2330 60-m fused sil ica capillary column.
The samples were also analyzed for the halogenated volatile organicpriority pollutants by Method 8010, and for the semvolatne organic prioritypollutants by Method 8270.
3.2.6 Procedures for Physical Characterization of Waste
Bulk density of the waste was determined by measuring the weight of aknown volume of this material at 20°C. Determination of heat of combustionwas by bomb colorimeter in accordance with ASTM 0 240-76. Determination oftotal solid and ash content was In accordance with protocols outlined inEPA/SW-846, 2nd Edition, July 1982.
3.2.7 Procedures for the Elemental Analysis of Waste and Hater Samples
One sample of the waste and duplicate samples of the scrubber tlowdownwater were forwarded to an outside laboratory for priority pollutant traceelement analysts. The methods used are summarized in Table 11. The wastesample was add digested in accordance with Method 3030, prior to analysis.
TABLE 11. ELEMENTAL ANALYSIS PROCEDURES USED
Element Analysis principleSW-846Method
Antimony, SbArsenic, AsBeryllium, BeCadmium, CdChromium, CrCopper, CuLead, PbMercury, HgNickel, N1Selenium, SeSilver. AgThallium. TlZinc. Zn
Hydride Generation Atomic Absorption 7041Hydride Generation Atomic Absorption 7061Inductively Coupled Argon Plasma 6010Graphite Furnace Atomic Absorption 7131Graphite Furnace Atomic Absorption 7191Graphite Furnace Atomic Absorption . 7211Graphite Furnace Atomic Absorption 7421Cold Vapor Hydride Generation Atomic Absorption 7470Graphite Furnace Atomic Absorption 7521Hydride Generation Atomic Absorption 7741Graphite Furnace Atomic Absorption 7761Graphite Furnace Atomic Absorption 7841Flame Atomic Absorption 7950
37
REFERENCES
3. "ASME MM5 Sampling Methodology for Chlorinated Organics," Draft No. 4,American Society of Mechanical Engineers, New York, October 1984.
4. "Analytical Procedures to Assay Stack Effluent Samples and ResidualCombustion Products for Polychlorinated Oibenzo-p-dioxins (PCOOs) andPolychlorinated Dibenzofurans (PCDPs)," ASME Environmental StandardsWorkshop, September 18, 1984.
38
SECTION 4
TEST RESULTS
Results of the tests performed are discussed 1n this section. TheInitial background burn results are presented In Section 4.1; Section 4.2describes results from the mini burn performed on September 9; full-burn testresults (September 20 and 21) are discussed in Section 4.3; calculated wastedestruction and removal efficiencies are discussed in Section 4.4; andanalysis results for the incinerator ash and scrubber blowdown are presentedin Section 4.5. ^
C\J4.1 BACKGROUND BURN
Figure 11 shows the continuous monitor data for the background burntests performed on September 4, 1985. The data plotted represent twenty °minute to hourly averages over the time period at the point plotted. Data 0taken at both the afterburner exit and the stack are shown. During thistest, instrument malfunctions necessitated that CO^ and Og be monitored byone Instrument for each parameter on a time-share basis. Thus, onlyafterburner data for COg and 0^ were recorded before 1300. and only stackdata were recorded after 1300. Problems with one N0^ analyzer limited dataacquisition for that parameter to the afterburner exit only. Problems withone CO instrument limited the acquisition of CO data to the stack. NeitherTHC nor HC1 levels were monitored during this test,
The data in Figure 11 show that Og and COg levels at the afterburnerexit averaged about 15 percent and 8 percent, respectively. NOx levels atthis location were generally below 40 ppm.
At the stack, O? and CO? levels were about 17 percent and 7 percent,respectively, from 1300 to 1900. Levels of CO in the stack were recorded aszero throughout the test, which suggests they were quite low, <10 ppm.
As noted In Section 3.1, MM5 sampling for paniculate emissions and POHC(2.3,7.8-TCDU) emissions was performed at the kiln exit. the afterburnerexit, in the E-duct (the horizontal transfer duct between the packed towerscrubber exit and the carbon-bed absorber), and at the stack (downstream ofthe ID fan). Two trains were run at each of the kiln exit, afterburner exit,and stack locations. Four trains were run in the E-duct. Correspondingsampling periods for each train were noted in Figure 11. As shown, alltrains ran uninterrupted for 8 to 10 hours except the one in the stack southport.
39
tf5 Train Ooftfinq ^IKS
5t*
SttE-aiE-aE-aE-<1AftAft)MlK11
18
16
S- ^sU 1 9
£.5 lc)
S
=~ '6
«
16
16
1 l<
g. 12
e- 10u
e" «6
4
C» Ml- ' — — • — — - — — — — — — — — — — — • — — — — • — — — " '
n 2 ,——————————————————————.
n 1 ————————————————————i 1 1 ( 1 1
- 0 Oz ——^T. Suck& CO;
- 0 coD NOx
/
( Aft«r6urt»r «x1t
o—o—o^^o—oo •
H
t i l t i i
0800 1000 1200 1400 . 1600 18CO 2000
T1—
m
70 mM (M
SO « 'r"& 0
40^ o
30 s °
i20
10
C
70
60
50
..iS
30 .
S'20
10
0
Figure 11. Emission monitor data: background burn of September 4, 1985.
40
Paniculate and 2,3,7,8-TCDD emission results are summarized inTable 12. along with results of the percent isokinetic calculation for eachtrain for which this parameter is applicable (no attempt at performingisok-inetic sampling nor duct traversing was made for the trains operated atthe kiln and afterburner exi ts) . As Indicated in Table 12, the percentisokinetic values for the trains run at the E-duct and stack locations variedfrom 62 to 101 percent. Only two trains were within the Method 5 specifiedacceptable range of 90 to 110 percent. Those trains fail ing this criterionfailed on the low side (percent I <90). This means that the velocity of thesample entering the probe nozzle was, on average, less than that of thecombustion gas sampled. The reason for these low values was that excessivepressure drop across the glass frit In the condenser/resin cartridge of thesampling train was frequently experienced. Thus, particulate emission levelsmeasured are likely to be slightly lower than those actually present.
The data in Table 12 suggest that paniculate levels In the kiln andafterburner exit were In the 0.3- to 3-mg/dson range as measured. OP 2 to8 mg/dscm at 7-percent QZ. At the stack exit particulate levels may have \0
been In the 2-mg/dson range, or 8 ng/dscm at 7-percent Og, although there was C\J
quite a difference in the measured loading between the two trains run. In T-any event, emissions were well below the 180 mg/dson corrected to 7,-percent QQZ limit 1n the CRF Part B permit. —
Dioxin levels measured were less than detectable 1 n all trains. This Is °as would be expected for the background burn. Detection limits 1 n the E-ductand stack were 1 n the 0.1 to 0.3-ng/dscm range.
4.2 MINIBURN
Figure 12 shows the continuous monitor data for the mini waste burnperformed on September 9, 1985. Again, data taken at both the afterburnerexit and the stack are shown. During this test. Instrument problems requiredthat QZ In the stack and afterburner be monitored on a time-share basis.Thus, 02 was measured at the afterburner exit from 0900 to 1500, and at thestack from 1500 to 2000. The instrument used to monitor N0^ 1n the stack washampered by a teak. As a consequence, no data were available until 1500, andnone were taken after 1700. A problem with the instrument monitoring COg inthe stack reduced the amount of useful data from the sampling location, suchthat no information was available after 1100. Instrument problems alsolimited CO data to the afterburner exit location. The THC monitor was alsonot run during this test.
Superimposed onto Figure 12 is the measured waste feedrate for the testduration, as well as an Indication of when sampling trains were run. Forthese tests, sampling train cooling system problems prevented performing MM5sampling at both the E-duct and stack locations. Sampling at the kiln exit(two trains) and at the afterburner exit (two trains) was performed.however.
The data in Figure 12 show that afterburner exit CO^ fluctuated between6 and 7 percent. Afterburner exit QZ Increased from about 12 percent at 1530
41
TABLE 12. PARTICULATE AND 2,3.7,8-TCDO EMISSIONS:OF SEPTEMBER 4, 1985
BACKGROUND BURN
S«uilin;locution'
VolutU«ul*«
(dial)»»ft»nt
Uo*in«tic
PtrciculH*—<9rrc(•y)
AS i(•9/uai)
wiiurwCorfcffl7.»»fC»nt(1/BtCB
to
^
Tot»l2.3,7.8-TCOOCSlltCtM(f»9/ir*1r»)
!.3.7.6-'CiO—iisions(n«/asca)
Kiln CXK
Tr»in 1Tr»in Z
Aft«roum«r exit
TC»<B 1Tfin ?
E-4UCT
Top tf»1nlOtlGB tr»1nLeft trilnItlgttt tr*io
Stack
EftSt tr»lnSautn triln
6.466.as
(.89i.U
S.SB9.W7.606.31
».771.71
n.o101. S12.7U.t
C.417.(
1.1I.*
5.720.1
_•_*..*
II.31.1
0.21O.M
0.133.4
2.30.4
••Itl.«c
«.6<2.S
<12<2.i
<1.2<2.3<2.3<2.0
<2.0<C.»4
<0.»5<0.36
<1.74.43
<0.11<0.2«<0.31<0.3l
<0.21<0.10
•»*i-t1cu)*l» —lint* not •MturM, no fllfr* i^CofTtCffl frvu It-ptrcwi 0; 10 7-DTcwt 0;.'Corrtcua frf l7-p«rc«»it Oj to 7-pTfBl 0;.
•r« uwd In W E-4UCX trxins for CT1» ft.
42
*^t«fttum«r 2A^tTBumtP 1
Kiln 2Min I
Figure 12. Emission monitor data: m1n1burn of September 9, 1985.
43
to over 18 percent after 1800. NOx levels at the afterburner exit weregenerally below 70 ppm. CO levels were also measured at zero during thistest, implying that they were less than 10 ppm. At the stack, 0^ levelsfluctuated between 16 and 19 percent up until 1500 when the location waschanged to sampling at the afterburner exit. NOx levels at the stack were inthe 20- to 35-ppn range for the brief period of time they were measured.
Paniculate and 2,3,7,8-TCDO emission results for these tests from thekiln and afterburner exit trains are summarized in Table 13. Recall thatthese trains did not sample isokinetically, so particulate levels should beconsidered only approximate. The data suggest that paniculate levels wereIn the 200- to 500-mg/dscro range In the kiln transfer duct and in the 600- to2000-mg/dscm range at the afterburner exit. Since no E-duct or stacksampling was successful for this test, a determination as to whethercompliance with a permit level of 180 mg/dscm at 7-percent Og could not bemade.
01ox1n levels measured at both the kiln and afterburner exit for thistest were also less than detectable, and at detection limits comparable to,to an order of magnitude higher than were realized during the background burn(e.g.. about 1 to 10 ng/dson for this test).
HC1 emissions were measured using the continuous CEA HC1 monitor at theE-duct location for these tests. The average concentration over the testperiod was 360 ppm, which corresponds to 0.54-g/dscm HC1. Afterburner exitflue gas flowrate was about 14 dsem/min for this test (see Section 4.4; no
TABLE 13. PARTICULATE AND 2,3.7.8-TCDO EMISSIONS; MINIBURN OFSEPTEMBER 9. 1985
Sampi1nglocation
Volumesampled(dson)
Particulateweight
(ing)
Particulatelevel
(mg/dscm)
Total2.3.7.8-TCODcollected(ng/train)
2.3.7,8-TCOOlevel
(ng/dson)
Kiln exit
Train 1Train 2
Afterburnerexit
Train 1Train 2
1.891.44
1.240.57
876.7257.5
723.61159.2
463175
5852030
<1.4<2.0
<16.3<6.2
<0.74<1.4
<13<11
44
E-duct flowrate measurement was made since the Method 5 trains were notoperated). If this were the E-duct gas flowrate, then the E-duct HC1flowrate would have been about 0.45 kg/hr. This 1 s below the CRF Part Bemission level of 0.5 kg/hr. However, clear compliance with the permitrequirement would have been better demonstrated if an actual E-duct flue gasflowrate had been obtained.
4.3 FULL BURN
Figure 13 shows the continuous monitor data for the first full wasteburn performed on September 20, 1985. Figure 14 shows analogous data for thesecond full waste burn performed on September 21. As for previous tests,data were taken both at the afterburner exit and at the stack* Data fromboth locations are shown in Figures 13 and 14.
Continuing difficulties with the continuous'emission monitor systemslimited stack data to COg levels only on September 20, although the fullcomplement of instruments was available at the afterburner for most of the otest on September 20. As shown in Figure 13, stack' CO? averaged about ^8 percent over the test, although stack CO? apparently steadily decreasedfrom about 9 percent at the beginning of the test to just below 8 percent v"near the end of the test. This steady decrease parallels a steady decrease 0in the nominal waste feedrate over the test, which Is also shown in oFigure 13. Nominal waste feedrate steadily decreased from the 15- to Q25-kg/hr range early In the test to below 5 kg/hr near the end of the test.Interestingly, a sharp drop In waste feedrate to zero in the middle of thetest (at about 1500) 1s accompanied by an abrupt, though -slight, decrease instack CO?.
Afterburner exit O? and CO? were quite variable over the test, with O?ranging from 6 to 12 percent and CO? ranging from 2 to 7 percent. The factthat the O? and CO? traces at the afterburner exit were parallel early In thetest (both decreasing or both Increasing In parallel) 1s highly suspicious.This implies that one (or both) monitors was reading erroneously. Furtherdisturbing 1 s the fact that stack CO? readings were greater than afterburnerexit levels over much of the test. The reverse Is expected owing to airinleakage between the two sanding locations. The fact that the afterburnerexit measured level was tower suggests that there was an air inleak in thesample transfer line to the analyzer. MOx emissions at the afterburner exitwere generally below 15 pom for most of the test. The CO monitor read zeroat the afterburner exit for the entire test, suggesting that CO levels atthis location were less than 10 ppn.
The Instrument problems in the analyzer system dedicated to the stacklocation which existed on September 20 persisted Into September 21. However,for this test the afterburner exit O? monitor was switched to monitoringstack gas at just about the time the flue gas sampling trains were started.Thus, as Illustrated In Figure 14. O? and CO? data were obtained at the stackfor the test duration, and CO?, CO, and NOx data were obtained at theafterburner exit over much of the test.
45
Stick ttl'.
Stack soutiE-ouct '.apE-auct '•ignxE-fluct oottatiE-duci 1»<l*ft«r&urn»r 2*ftertturn«r 1Kiln 2Kiln 2
25
20 h
15 •
10 -
5 -
0
0-0
0
50
40
30
20
10
0
e>
Figure 13. Emission monitor data: fun burn of September 20, 1985.
46
Suck ««stSuck southE-auc-: too£-<3uCt rigfttE-oue-: &OIMB£-<3ud liftAftersumT 2Aftergumer 1< i1n 2min i
1200 1400 1600 18GO 2000 Z200 2400 OZOQ 0«00
Figure 14. Emission monitor data: fun burn of September 21, 1985.
47
Figure 14 shows that stack Og and COg levels were about 14 and7.5 percent, respectively, early in the test, with a relatively abrupt changeto about 12 and 8.8 percent, respectively, late in the test. At theafterburner exit, CO^ levels varied about 4 percent early in the test, overthe period during which the monitor was operational. Again, the fact thatstack CO^ levels were higher than afterburner exit CO^ levels is disturbingand suggests a continuing air inleak in the afterburner exit sample transferline. Afterburner exit NO)( levels were less than 20 ppm throughout the testfor the periods they were monitored.
THC levels were measured both at the Inlet and outlet of the carbon-bedabsorber during the September 20 test (continuing Instrument problemsprevented obtaining data on September 21)• These data are shown InFigure 15. As indicated, the THC levels at the carbon-bed inlet wereessentially level at 5 ppm until about 1900 when there was an apparentdecrease to 2 ppffl. This apparent decrease was due to an instrumentcalibration check, however, and not reflective of a real change in flue gasconcentrations. Carbon-bed inlet THC levels did spike once to 27 ppm at1630. THC levels at the carbon-bed outlet were about 4 ppm until 1400. ^decreasing to 2.5 ppm until 1900. There was a further apparent decrease tobelow 1 ppm at 1900, but this again was due to an instrument calibration fn
adjustment. Of course, all these levels are quite low, near the quantitation \~1 trait of the analyzer used. Q
Paniculate and 2,3,7,8-TCOO emission results from the full waste burn °test of September 20 are summarized in Table 14, along with results of the °percent isokinetic calculations for the E-duct and stack trains (the onlyones for which duct traversing and sampling velocity adjustments were made).An analogous sunmary for the full waste burn test of September 21 is given inTable 15. As indicated in Table 14, the percent Isokinetic values for thetrains run in the E-duct and the stack for the test on September 20, rangedfrom 72 to 94.5 percent. Only fop two trains was the percent isokineticvalue between the 90 to 110 percent requirements for an approved paniculateload measurement via Method 5. The reason for the tow values again wasexcessive pressure drop in the condenser/resin cartridge of the train due toplugging of the glass frit in this cartridge as noted in Section 4.1.
These deficiencies aside, paniculate levels in the E-duct were343 mg/dscm based on averaging the levels measured by an four trains. Siventhat the flue gas 0^ level at this location was liable to be in the10-percent range (see Figure 13, afterburner exit), paniculate levels atthis location, were they direct emissions to the atmosphere, would exceed theRCRA hazardous waste incinerator performance standard of 180 ng/dscmcorrected to 7-percent Og. However, levels measured at the stack location,downstream of the carbon-bed/HEPA filter, were 47 ng/dson (average of the twotrains operated at that location). Although no stack O? data were availableat this location for correcting emissions to 7-percent Og, 1f stack Oz levelswere less than 17.3 percent, then paniculate emissions would have been lessthan 180 mg/dsoa corrected to 7-percent Og. Since afterburner exit O? levelswere less than 11 percent for these tests, it Is expected that stack O?levels cenainly were less than 17 percent, thus paniculate emission Tevels
48
1000 1200 1400 1600 1800 2000T1«e
2200 2400
Figure 15. THC monitor data: full bupn of September 20. 1985.
49
TABLE 14. PARTICULATE AND 2,3,7,8-TCDD EMISSIONS:SEPTEMBER 20, 1985
FULL BURN OF
S^nia^nslocation
Volumesame 1<a(dsea)
PtrcentItOKinttic
P»r-:'ieu'>*itxtignt(1)
P*rtieu1ateeinsnons
«! —tSUl-M(•9/escin)
Tot*12,3,7.8--;00conte-.efl(r»9/tr»in;
2.2.7,8-':;0emissions(ng/ascBi)
K i l n »xit
Tr«1n 1 4.36 ~ 11.8 2.71 <2.< <0.55Trun 2 7.53 — 11.0 1.46 <1.3 <0.17*»»r»9» 2.09
AfttPBunrr »x1t
Tnin I 1.41 • — S22.8 371 <S.3 <3.8Tr»1n 2 3.34 — 10.5 —* <4.2 <1.3
E-auct
Top train 6.82 94.5 796.5 266° <2.9 <0.43Botia« tf»1n 4.31 73.4 829.3 5640 <2.2 <0.51K1.(ni tr«ln 5.13 62.0 564.3 291° <l2.7 <2.5Left triln 5.64 88.5 511.4 2510 O.I ,<Q.55Av«ray« 343
Sfck
Ettt tn'tnSoutn crilnAvriyc
7.426.31
93.774.5
284.8353.5
38.456.047.2
<16.80.3
<2.3<1.5
*Evta«ne» of tignlflcint 1«ik In tn« SJapllna trfin —s discovertd «ftcr U)ip11n9 MISew\stt. Diti considTtd <nv«11d for (xrticul*l« ••uuriMnti.
^Trnn f1U»n rc«ov«« prior u tft< ca«p1(t1on of suwiing; volufri uap1*4 with fllfrs Inplic* —rt 3.0, 1.47, 1.94, ind 2.01 ascr, r»s»»ct1»»)y. for tir up, bottcr, right, tnd1«ft tr»ln». r«sp«ct1vlJr.
50
TABLE 15. PARTICIPATE AND 2,3,7,8-TCDD EMISSIONS: FULL BURN OFSEPTEMBER 21, 1985
Toil I«0lu— »»rt1eul*l« Carr»ei«a to 2.1.7,a-TC30 2,3,7.3-TCSO
S«BuIii<J s—plM P«rc»nt —iqnt At —SUCM 7-pTCtni 0^ calltCtM insionslocation (asa) f»ox)n«tie (•q) (•q/dsa) (•q/aical (nq/tron) (ng/aieal
Ki ln «x1t
Tr»1n I 1.01Tnin 2 0.3S
AflTBurnT •xit
Tnin 1 3.90Tntn 2 2.fBA—r*4«
E uet
M2.3 7S3(70.0 1940
SM.9 1S4S12.5 199
l7»
<«.! <«.«<y.2 <2l
<l5.0 <}.«<7.3 <2.< \0
^Top tfin (.72 t7.» <l <0.ljlattw tratu 5.97 31.2 U.( 2.3(lain tr»ln S.SO 37.4 ».( 10.1rrt tr«l« 7.$» 40.C <l <0.l3
SUcx
<l2.9 <l.» /-^<l2.0 <2.0 '~'<U.3 ' <2.2 0<!.» <0.7B
0
Ewt tr«ln S.6B S3.2 «12.0 72.* 132l «.3 <l.S&Mtn u-tiR 2.78 U.I S77.7 201 378« <4.J <l.(Avrty 140 2SS
•Corfcfa u 7-»»fc«nt Ot 'w « »wr fua ^ l«r«l •f U.3 pwxMt. —• MgBra «-4.
51
should have been In compliance with the CRF Part B particulate emissionlimit.
iAs in previous tests in this series, dioxin levels were less than
detectable in all individual train extracts analyzed. The data in Table 14suggest that dioxin (2.3,7,8-TCDO) levels were less than aoout 0.5 ng/dscin atthe kiln exit and in the E-duct, less than the 1- to 4-ng/dson range at theafterburner exit, and less than about 2 ny/dscn in the stack. OREimplications of these results are discussed in Section 4.4.
- The data 1n Table 15 show that the attempts to perform isokineticsampling in the full waste test burn on September 21 were less successfulthan those in the tests on September 20. The percent Isokinetic values forthe E-duct and stack trains ranged from 31 to 53 percent during this secondset of tests. In addition, many other problems were associated withobtaining partlculate levels in the E-duct for this test. In fact. two MM5train filters actually apparently lost weight after sampling. As a result, r"-the paniculate loading data at this location are not considered reliable in ^the slightest. .
Particulate emissions at the stack were 140 mg/dson as measured (average °of the two trains operated at this location), or 255 ng/dscm corrected to 07-percent O^. This level 1 s greater than the RCRA hazardous waste oIncinerator partlculate emission standard and the CRF Part B permit emissionstandard of 180 ng/dscm at 7-percent Og.
Again no dioxin levels were found above method detection limits In thecombined (single train), extracts from any sampling train run. Thus. dioxinlevels were less than 4 ng/dscm at the afterburner exit, less than 2 ng/dscmIn the E-duct. and less than 1.5 ng/dscm In the stack. Section 4.4 discussesthe ORE Implications of these results.
HC1 levels In the E-duct were measured via two techniques during thetest on September 20. These were by way of the CEA continuous HC1 monitordescribed in Section 3.1, and by analyzing the MM5 train Impinger solutionsfor captured chloride via specific Ion electrode. The average CEA analyzerreading over the test period was 160 pom HC1, which corresponds to0.25 g/dson. Th.e HC1 levels 1n the E-duct as determined by the MM5 trainImpinger solution analyses were 0.21, 0.22, 0.31, and 0.29 g/dscm for thetop, right, bottom, and left trains, respectively. Thus. the average MM5train value was also 0.26 g/dscm HC1* The E-duct flue gas flowrate wasbetween 13 and 18 dscm/ain (see Section 4.4). depending on whether more trustwas placed In a Method 5-related velocity traverse (18 dscm/min) or thehelium tracer system measure (13 dsca/min). Thus, E-duct HC1 flowrates, at0.26 g/dson concentration, were between 0,2 and 0.25 kg/hr. If these werestack emission rates (stack emissions should be the same as E-ductfiowrates). then they were well below the CRF Part B permit requirement of0,5 kg/hr.
52
4.4 O I O X I N ORES
DREs for POHCs In a trial burn such as the ones performed 1 n this studyare typically calculated by dividing the flue gas mass flowrate of POHC (asdetermined by the flue gas sampling procedure used) by the mass flowrate ofPOHC fed to the incinerator (as determined by the waste feedrate and thewaste POHC concentration), subtracting this value from 1.0 and multiplyingthe result by 100 (to give a percent value). However, as il lustrated by thedata shown in Figure 12, 13, and 14, the waste feedrate varied considerablyover the duration of each test performed. As a consequence, a slightlydifferent procedure was used to calculate DREs for this set of tests.Instead of using waste feedrates and flue gas emission rates, the totalquantity of waste (POHC) fed during the period of time a given sampling trainwas In operation was divided by the total expected amount of POHC emittedover that time as calculated from the sampling train data, and this ratiosubtracted from 1.0 and multiplied by 100.
The total amount of waste fed over a given sampling Interval was taken 00directly from the waste Tote tank scale readings recorded over time. Results [of the analysis of three waste samples taken before and during the tests ,--showed 2.3.7.8-TCDD concentrations of 32» 29» and 49 ug/g waste, for an —average of 37 ug/g. '
0The total amount of POHCs emitted was calculated from the concentration, 0
as measured by the respective sampling train, multiplied by an estimated fluegas flowrate and by the period of time the respective sampling train was Inoperation. The estimated flue gas flowrate was obtained via two methods.The first was from the MM5 train flue gas velocity measurement, which wasused for a11 sampling locations. The second was frora the helium tracer datawhich allowed a backup calculation at the E-duct and stack samplinglocations.
ORE results calculated via these methods are shown 1n Table 16 for theminiburn of September 9, In Table 17 for the full burn of September 2U, andIn Table 18 for the full burn of September 21.
The data 1 n Table 16 shows that the detection limits achieved in samplesfrom the kiln exit sampling trains allowed establishing that 2,3.7,8-TCOOdestruction efficiency (DE) was greater than 99.9999 percent in the kiln forthe mini burn performed on September 9. The poorer detection limits achievedIn afterburner exit sampling trains, combined with Increased flue gasflowrate at this location, resulted In the ability only to establish combinedkiln/afterburner DE of greater than 99.9998 percent.
Table 17 suggests similar conclusions from the full bum tests ofSeptember 20* Again OE of greater than 99.9999 percent was apparent at thekiln exit. However, only greater than 99,999 percent DE could be establishedat the afterburner exit. 6ood detection capabilities In three of the fourIndividual E-duct trains suggest that Incinerator system (k11n, afterburner,and APCD) ORE was greater than 99.9998 percent regardless of which flue gasflowrate measure is used (the helium tracer method flue gas flowrate value
53
TABLE 16. 2,3,7,8-TCDD DREs: MINIBURN OF SEPTEMBER 9, 1985
SOT^Iinyloctfion
Kiln exit
Triln 1Tr»1n 2
Afterburnertxll
Tr«in 1Tr»1n 2
*B«sed on —St* 2.3.7.11-TCOO
TTo^al —o
•flnun; of 2,3.uaste f«d
(kg)
7777
7777
Ot»lunt of7,8-TOf«<»*(a)
2.92.9
2.92.9
conc»ntr*t1of> of
Stapling0 perioa
aur»non(•in)
251261
261261
Hue 9*s2.3.7,8-TCODconct"tr»tion
(ng/flSOB)
<0.7*<1.4
<l3<n
37 m/g.
&asea or
Flue g*sflo«rite
(aso»/«in)
7.S7.5
13.713.7
.
ntlluBi tr«(
Toul2.3,7.8-TCOt
WIttW(wg)
<!.<<2.7
<46<39
'
:er <Mf*
iORE
(percent)
>99.99995>99.W991
0^X9.9984 i>99.9886 —
0
0
0
54
TABLE 17. 2,3.7,8-TCIM) ORES: FULL WASTE BURN W SEPTEMBER 20. 1985
s«,i4i(•CttI——
Rlla ilk
leal* Ilr«l« 2
AUftwwr•*ll
lr*ln »lr«l« 1
l-*Ml
t— tr«l«toil— triteMM tr»t«
5; rh»r«i«
StKk
(Ml IraldiMlk U-*l«
IMII
—if r«4(»•>
n•l
n<i
uuuM
UM
11*1
I.l.f.l )C«(*4*(«)
1.41.4
1.41.4
(.•t.«t.H<••
I.It.«
**"»!'?r*rl*4*ir*ll—(•(•)
tf»>•
»HtM
4M4M4M4S*
4M4h)
fll— •**t.i.r.i-Kuoc—<«i»tr*ll—
(•»/41C)
<«.H<•.)?
«1.«O.I
<«.41O.ll<(.»<«.M
«.l<1.1
Flm ft(lour*!*
(4tC/Bl>)
••I••<
IS.IIS.I
r.ir.ir.ir.i
M.IM.I
Kf4 •• h*llr lr«c«
Itt)f.i.r.a-icu)••llf4
In)
«.•<••>«
<it<ll
41.1«4.1<M<«.»
<n<14
r 4*r
M(<p«rc*«t)
>—.«W*f>••.««««•
•
>—.«*M)>—.««Wf
>««.*mi>*•.«««?«tIt.tWU>*».»M»»
m.mol>««.tM4S
•«»«4 —
flu* t*l(luMrd*
(Jicr/air)
..
..
1 1 . 111.11 1 . 111 .1
r.ir.i
(In
(01 «1t.i.r.* icuu
— 1 1 1 * 4l^t
• (*1 ••
--
--
<2.i<).o<IS<1.2
<11< 1 )
lu
>««.«««•>>««.«n8&>M.<WS>«<.«41B1
>w.«mt>««.99»1
lly di«
Ml(per >.<«(>
--
--
•U* t.l.f^-KW cwlr*ll— •( W —/•.
0 0 0 1 4 0
differs from the Method 5 pitot tube velocity traverse value by 20 to30 percent at the E-duct, as discussed 1 n Section 2.3; this difference wouldnot measurably affect ORE. e.g., the difference between 99.9998 and99.9999 percent ORE corresponds to a factor of 2 difference in flue gasf lowrate estimate). Poorer detection limits for the stack trains allowedonly establishing final (full system) ORE of greater than 99.999 percent.
Table 18 again shows similar conclusions for the full burn performed onSeptember 21. Here the data suggest incinerator system 2,3,7,8-TCOD ORE ofgreater than 99.9997 percent in both the E-duct and the stack.
The current regulations for dioxin destruction via incineration require99.9999 percent ORE. Accordingly, the objective of these tests was toinvestigate whether this level could be achieved. Based on the single trainresults presented 1n Tables 16 through 18. It can be stated that. 1n a 1 1likelihood, 99.9999 percent ORE was achieved. However, clear demonstrationof this was not possible on an Individual train basis due to methoddetectability limitations. • .
In an attempt to lower detection limits to be able to make anunambiguous 99.9999 percent ORE capability statement, the extracts.from thefour E-duct trains for each full burn test were combined, furtherconcentrated, and subjected to method cleanup procedures. These further 0concentrated, pooled extracts were analyzed via HR6C/LRMS for 2,3,7,8-TCDO. oResults from these analyses for the September 21 full burn are summarized In QTable 19. As shown 1n the table, 2.3,7,8-TCDD was not detected even in thecombined extract from the four MM5 trains operated at. this location for thistest. Results from the pooled September 21 test E-duet MM5 train extractsshow that about 99.99999 percent ORE was achieved upstream of the carbon bedabsorber for this test. This Is an order of magnitude greater than therequired 99.9999 percent ORE.
The usefulness of data from the pooled E-duct trains taken September 20Is severely compromised due to a spiking error which occurred during theoffsite preparation of these extracts. A 10- to 15-fold excess of a recoverystandard ^Ciz-ltZ^^-TCDO. was added to each of these extracts. Injectionof such gross quantities of this compound saturates the mass spectrometer andoverloads the capillary GC column within the retention tine window of native2,3,7,8-TCOO, precluding measurements of this analyte at low levels. As aconsequence, the detection limits for pooled extracts (ng/dson of flue gas)are not significantly below those for individual train extracts, thus littlemore can be said regarding 2.3,7,8-TCDO ORE for this test beyond conclusionsstated In Table 17.
4.5 INCINERATOR ASH AND SCRUBBER SLOWDOWN ANALYSIS
Over the course of the three waste burns, approximately 26,5001.(7000 gal) of scrubber blowdown was collected In two temporary storage tanksbrought into the CRF specifically for this purpose. One tank contained a^out15.100L (4000 gal) and the other about 11.400L (3000 gal). After the tests.two 2L samples of composited scrubber blowdown were collected. These were
56
TABLE 18. 2,3,7,8-TCDU ORES: FULL WASTE BURN OF SEPTEMBER 21, 19H5
s-riiirIKUI—
Kiln ult
fr*lr Ilr*lr I
AllTbwr•*lt
Irilr |(r«li t
l-*Kt
If trait••It— tr*l•Itfkl ((•*••l«lt lr*l*
U«ck
(itt tr«l«S—tll lr«ln
*««**4 •• «—1« I.l.I.l-ICUO &
TABLE 19.
t.i(•*! ITM 1
(•II Mf•( </»/H
If) —«——t •( 2,1
—tf 1*4(ktfl
4»41
letlot
in• ifl
ir«u«
1*4isa
i«t*i ifi—nl •( ml—.(.•-ICW SMvl*rt |«) («»•»
•.« n.n
lotilMMX •f &
.».«-ttt0 )1*4* *<t> 1
l.tl.i
1.1l.«
«.«t.41.4t.i
••11.1
MK—lr*ll—
2,3,7.8-TCDO OREs BASED
i«t«i'.).».•
C«ll*€tt4« («»/4
(r<lnt|
<i.r
•rili Frrl*4 S.Iirtll— c—1««»» (
14«140
my
«M<M•M«i6
»M(H
•* W m/9.
t.l,».»-IC••liii—t(i/-»i-(
<«.M6
1— ••*.».«-ICBBCMtrttI—i-/4ica| (
<t.4«1
<!.««f.«
<!.««••«».»<«.»
«.»<l.t
SfiiirM p*rlo4
•hirfti—(-•"»
•M
•«««4 11
flu* •*» 11 (««•((•lIlf/Bll)
«•>••»
ll.i11. i
li.lli.l16.116.1
U.St».l
ON E-DUCT COMBINED HM5
•*t*4 •
ri— «•<tl—r*f
|4«c«/«l«)
It.l
•Mil— lr«<
(•1*1!.•».».•-ICU
••111*4(M)
<«••<ro
<i»<it
«M<tl<fl0.0
€|S
<t»
• (•II— (r*c«r 4*f
(•Ctl».*.».«-«<
—<11*4<•«)
<0.<«
:«r 4*1 •
1—(
(r«rc«rl) i
>»1.W»«>W.M»M
>—.«t*U>M.WW
>—.MM«>•«.«**»>>««.««M4k—— —————fTf* •U——
>*».»*»»»>««.*WfI
XDMf
(ptrcert)
^^ •mm
••lt4 an'
Flu* ft(l(Mr*l*
|4tci/rl«)
11.411.411 .411 .4
!>.()>.»
TRAIN EXTRACTS
••t«4 —
(>«• (•1llawrtf(4*c.»
» 11 .4
flu* y*» «•
larlZ,l.».» 1C
fll(*4(^>
< 1 »or<l»<«•>
<liOS
llm 1*1 •i
l«t*lI.l.».»-ltl
frlll*d(-I)
<n.4»
1
l
tlucftf 4*1«
1
llMlly <lJt«
M)Wll
(pencnl)
»»».»•»•»><>«*.M41I>««.««tf0>M.OT •1B'»»
>»».»•»»>«>«t.i«tn
Min
(pricrni)
•It.WWI
0 0 0 1 4 2
sampled from the top of each tank while contents were being recirculated.Sample containers for collection and shipment were rigorously cleaned at theEnvironmental Compliance Laboratory, Bay St. Louis, Mississippi (ECL-BSL).
In addition, a quantity of ash accumulated in the kiln ash pit over theduration of the experiments. Eight 50g samples of this ash were alsocollected.
Four ash samples were forwarded to Battelle-Columbus Laboratories foranalysis of 2,3,7,8-tetra-, total tetra-, penta-, hexa-, hepta-, andocta-CDOs and CDFs via the methods noted In Section 3.2. The two watersamples were forwarded to ECL-BCL for extraction and extract cleanup, withextracts in turn forwarded to the Environmental Monitoring SystemsLaboratory, Research Triangle Park. North Carolina (EMSL-RTP) for analogousPCDO/PCDF analysis. Results of these analyses are given 1n Tables 20 and 21.Values in parentheses In the tables reflect the method limit of detection for ^samples in which a particular chlorination class was not detected.
The data in Table 20 indicate that the kiln ash samples were devoid of • v-
tetra-, penta-, hexa-, hepta-, and octa-CDOs and CDFs with one possible 0exception (possible presence of octa-CDO). The data in Table 21 show that othe scrubber blowdown water samples were also devoid of tetra-, penta-, ,-.hexa-, hepta-, and octa-CDDs and COFs with the exception of octa-CDOs whichwere present at the 70 ppt level. This Is not surprising since octa-COOs arerelatively common in environmental samples.
As noted in Section 3.2, the scrubber blowdown was also analyzed for theorganic arid trace element priority pollutants. Results of these analyses aresummarized In Table 22. As shown In the table, none of the organic prioritypollutants are present In the blowdown at levels above 100 ppn. In addition,none of the trace elements are present at concentrations which would causethe blowdown to be considered EP (Extraction Procedure) toxic. Based on allthe analytical data, the blowdown would not be considered a hazardous waste*
58
TABLE 20. LEVELS OF PCDD AND PCDF IN KILN ASH SAMPLES
Concentration3 (ppt)^
Analyte
2.3.7.8-TCOOTCDDs-CDOPenta-CDDsHexa-CCDsHepta-CDOsOcta-CDDs
2.3.7.8-TCDFTCDFsPenta-COFsHexa-CDFsHepta-CDFsOcta-COFs
Sanple 1
(13 )(13)(28)(7.4)(14)(44)
(7.0)(7.0)( 1 1 )(4.6)(12)(33)
Sample 2
(10)(10)(6.5)(4.5)(6.3)(18)
(16)(16)(2.7)(2.8)(6.2)(21)
Sample 3
(5.6)(5.6)(4.2)(5.0)(3.4)(15)
(7.1)(7.1)(1.7)(3.1)(3.4)(15)
Sample 4
(28)(28)(16)(37)(8.4)235
(10)(10)(6.4)(7.4)(8.4)(40)
•Numbers In parentheses denote analyte not detected tothe detection limit noted In parentheses.
b! ppt.• 1 pg/g.
59
TABLE 21. PRIORITY POLLUTANT COMPOSITION OF THE SCRUBBERSLOWDOWN WATER
Concentration3 (ppt^
Analyte
2.3,7.8-TCDOTCOOs-COOPenta-CODsHexa-CCDsHepta-CDOsOeta-COOs
2.3.7.8-TCOFTCDFsPenta-COFsHexa-CDFsHepta-COFsOcta-COFs
Sample I
(0.005)(0.06)(0.04)(0.03)(0.02)0.07
(0.02)(0.1)(0.02)(0.02)(0.1)(0.1)
Sample 1duplicate
(0.02)(0.08)(0.05)(0.04)(0.04)0.04
(0.01)(0.07)(0.02)(0.06)(0.02)(0.08)
Sample 2
(0.02)(0.09)(0.04)(0.04)(0.03)0.07
(0.02)(0.1)(0.07)(0.06)(0.03)(0.06)
Sample 2duplicate
(0.04)(0.09)(0.02)(0.03)(0.05)0.07
(0.02)(0.06)(0.03) /(0.06)(0.03)(0.04)
•Numbers In parentheses denote analyte not detected tothe detection limit noted 1n parentheses.
b! ppt • 1 pg/nl.
60
TABLE 22. PRIORITY POLLUTANT COMPOSITION OF THE SCRUBBER BLOWDOMN WATER
Concentrationa Detection limitComponent ( p p b , wt) ( p p b , wt)
Volat i le organic priority pollutants
Methylene chloride NO 12.61,1-dichloroethylene NO 2.61.1-dichloroethane 6.1 2.6t-l.2-d1ch1oroethy1ene NO 2.6Chloroform NO 4.21.2-dichloroethane NO 5.01.1.1-trlchloroethane NO 2.6Carbon tetrachloMde NO 2.6Bromochloromethane NO 4.21,2-dlchloropropylene NO 2.6t-l.3-dich1oropropy1ene NO 5.0Trichloroethylene NO 2.6Benzene NO . 2.61,1.2-trlchloroetnane NO 6.8BromofonB NO 4.2Tetrachloroetnylene + NO 5.0
tetrachloroethane.Chlorobenzene NO 12.6
Semlvolatne organic priority pollutants
All base/neutral sea1vo1at11e priority NO 5pollutants
4-ch1oro—3-niethy1 phenol NO 502.4,6-trlchlorophenol NO 302,4-dinltrophenol NO 304-nltrophenol NO 502-<nethy1-4,6-d1n1tropheno1 NO 50Pentachlorophenol NO 50An other add semlYolatne priority NO 10
pollutants
61
TABLE 22. (concluded)
ComponentConcentration^
(ppm, wt)Detection limit
(ppm, wt)
EP toxicityconcentrationlimit (ppm)
Trace elements
Antimony, SbArsenic, AsBeryllium, BeCadmium, CdChromium, CrCopper, CuLead, PbMercury, HgNickel, N1Selenium, SeSilver, AgThallium, T1Zinc. Zn
NDNDNONDNO4blbNOlt>NDNONONO
213111111111
10
—5
—15
—50.2
—15
—••
^D denotes not detected; duplicate samples analyzed,hpound in only one sample; not detected 1 n the others.
62
SECTION 5
CONCLUSIONS
A series of Incineration experiments was performed with the VertacChemical Company's toluene stiTlbottoms waste from trichlorophenolproduction. This waste Is one of the more well known of thedioxin-contaminated wastes presently in existence* Samples of the wastetested in this study contained an average of 37 ppro 2,3.7,8-TCDO (37 ug/g). 03
Three Incineration tests were performed during September of 1985. All "were performed in the CRF rotary kiln incineration system with waste feedrate \-
nomina'ny 20 kg/hr. , 0
With regard to the principal objectives of these tests, the followingcan be concluded: -
• 2,3,7,8-TCDD ORE based on the combined extracts from the four MM5trains at the v1tua1 stack was greater than 99.99999 percent for onetest. For the other test method detection limits preventedquantitating that better than 99.9998 percent ORE was achieved.
• Determination of paniculate emissions at both the virtual andsystem stack could not accurately be determined due to technical andoperational factors.
• Further research is needed, to establish the amount, nature, andsource of paniculate emissions from these sources.
• HC1 emissions In the virtual stack ranged from 0.2 to 0.45 kg/hr.These results are less than the RCRA standard of 1.8 kg/hr.
The above conclusions suggest that incineration should be considered aviable disposal •ethod for this still bottoms waste, given that appropriatesafeguards are employed. The data in this study confirm that an incinerator,operating under proper conditions, is capable of achieving 99.9999 percent2,3,7,8-TCOO ORE, with HC1 emissions below the regulatory limit.
63
SECTION 6
QUALITY ASSURANCE/QUALITY CONTROL
The most critical QA objectives for this test series were dictated bythe goal of the test series Itself. This goal was to demonstrate Incineratorcapability to destroy dioxin-contaninted wastes or, more specifically, todemonstrate a ORE of at least 99.9999 percent for 2,3,7,8-TCDO. C^
t^The determinants of ORE are mass feedrate of the POHC 1n the Influent ,_
waste (Q-in) and mass emission rate of the same POHC 1 n the output stack gas -^(Qout)' Thus, It was on the measurement of these quantities that QCactivities were most tightly focused during the CRF test series employing the °toluene still bottoms waste. In what follows, QC activities determine to the 0measurement of Qin and Qout w 1 1 1 be listed, explained, and evaluated asregards their effectiveness in defining the quality of the measurements made.Such evaluations win be based on precision, accuracy, and completeness,
6.1 MEASUREMENT OF Q-IN
Waste was fed to the incinerator from a stirred reservior, connected tothe feed pump with a flexible stainless steel line and mounted on theplatform of a continuous weigh scale whose remote readout was located in thecontrol room. Recordings of weight and clock time were taken at 10 to 30 minIntervals throughout periods when feed was being pumped to the kiln.HRtiC/LRMS analysis of preburn and inburn waste feed samples Indicated theaverage concentration of 2,3.7,8-TCDO in this material to be 37 ug/g. Thus,measurements of clasped time, change 1 n weight, and concentration constitutea complete set for calculation of Qin during any recorded Interval of wastefeed. The continuous weigh scale was calibrated in duplicate with knownweights yielding the result that its accuracy and precision were fixed by itsreading resolution of ±0.23 kg (0.5 Ib). Duplicate analyses of a waste feedsample for POHC concentration had duplicate results to two significantdigits, suggesting a high order of precision for this measurement. Asregards accuracy, surrogate recovery for these analyses averaged 92 percentwhile a standard analyzed with these samples yielded 115 percent recovery.
6.2 MEASUREMENT OF QQUT
Measurements of mass emission rates of 2,3,7,8-TCOO 1n the flue gas atvarious points In the CRF rotary kiln system were accomplished by extractingknown volumes of this gas using MM5 sampling trains equipped with heatedfilters and XAO-2 absorbent. Extracts were prepared from each component of a
64
given train (probe, filter and holder, sorbent, condensate catch, andconnecting lines), pooled, subjected to preliminary cleanup, and analyzed for2.3,7,8-TCDO by HRGC/LRMS. Stack gas flowrate was measured by pitot tube aswell as helium dilution.
The accuracy, precision, and completeness of stack gas sample volumemeasurements are supported by written calibration procedures anddocumentation of most recent calibration of equipment used to make thesemeasureinents. Method 5 data sheets, which are maintained for each sampletaken, record additional information used to calculate sample volumes and toensure the validity of sample taken. For example, barometric pressure andmeter temperature used for the former and resin temperature for the latter.
Contain! nation of sample extracts from glassware and reagents as Nell ascross-containi nation among trains may be severe problems when POHCdeterminations at the nanogram level are required to support ORE calculationson the order of 99.9999 percent. Possible contamination from glassware,reagents, and sample processing was monitored by submitting the extractharvested from a field blank train, along with extracts from the flue gas 0sampling trains for a given burn day, for POHC analysis. This field blank mtrain was assembled by the sampling crew on each burn day and Included all ^_typlcal train elements (probe, filter and holder, adsorbent, condensate catch —and connecting lines) except pump and meter box. In an effort to minimizecross-contamination among trains, several practices were adopted: 0
0• All samples from one burn cleared the laboratory before another burn
was undertaken
• All the glassware used to assemble a train as well as to process thesample extract harvested from It, constituted a unique set and werealways used together to take samples from the same Incineratorlocations
• A given train was processed from receipt In the laboratory to thefinished extract by one and only one worker
Three mechanisms were used to monitor accuracy of POHC analysis 1n fluegas samples:
• Use of a field spike train
• Inclusion of POHC surrogates In every sampling train
• Analysis of method standards with each batch of samples
The field spike train Is Identical with a field blank train with the additionof a 20-ng or 200-ng spike of native (unlabeled) 2,3,7,8-TCOO placed on theadsorbent (200 ng) or split between the adsorbent (1(J ng) and the Impingercondensate catch (10 ng). The 20-ng spike was recovered at 70 percent whilethe 20U-ng spike yielded 10 percent and 96 percent recovery, respectively.The second monitoring nechamism, use of surrogates, was Implemented by
65
placing 50 ng of ^C^-Z.S.P.S-TCDD and 10 ng of ^ClA-Z.a.y.S-TCDO in theXAD-2 bed of each MM5 sampling train just prior to harvesting an extract foranalysis from that train. Recoveries for the ^C^-Z.S.P.S-TCOO in all flueyas samples ranged from 12 to 104 percent with an average of 34 percent asshown in Table 23. Table 23 also shows that recoveries of the-^Cl4-2,3,7,8-TCDD surrogate relative to the Internal standard(^CI^^.P.S-TCUO) ranged frora 93 to 144 percent with an average of114 percent.
It should be emphasized that native (unlabeted) TCDD spiking and laoeledsurrogate spiking are overall recovery measures In that they measure theperformance of the entire process of harvesting an extract from the samplingtrain, through preanalysis cleanup of the extract, through GC/MS quantitationof the compounds of interest.
The final accuracy monitor CTployed was the analysis of a methodstandard, prepared 1n the 6C/MS laboratory, with each batch of incinerator T-samples. The recovery of this standard measures the performance of the mpreanalysis cleanup method as applied to a pure analytical grade standard ^_solution. The results for these standards were 111 percent, 44 percent, and159 percent recovery In three trials. • . °
00
66
TABLE 23. SURROGATE RECOVERIES IN THE ANALYSIS OF MM5 TRAIN EXTRACTS
^CIS^.S.V.S-TCDO 37C^4-2,3,7.8-TCUl]Sanple recovery (percent) recovery (percent)
September A , 1985 MM5 trainsKiln exit 1Kiln exit 2Afterburner exit 1Afterburner exit 2E-duct bottomE-duct topE-duct rightE-duct leftStack eastStack south
September 9, 1985 MM5 trainsKiln exit 1Kiln exit 2Afterburner exit 1Afterburner exit 2
September 20. 1985 MM5 trainsKiln exit 1Kilo exit 2Afterburner exit IAfterburner exit 2E-duct bottomE-duct topE-duct rightE-duct leftStack eastStack south
September 21, 1985 trainsKiln exit IK 1 1 n exit 2Afterburner exit IAfterburner exit 2E-duct bottomE-duct topE-duct rightE-duct leftStack eastStack south
21356225363144374843
60311817
373326343543
104312612
44411514191619372137
110117119117116
93111110108117
1131181 3 3 '121
116119109119111118116117142106
119113123116144136115129111113
Average 34 114
67
SECTION 7
HEALTH AND SAFETY
The procedures followed during these tests, which were designed toprotect the CRF staff and the nearby general population, were as documentedIn the test protocol document (5). As part of these procedures, severalenvironmental ambient air samples were taken during the course of the testprogram, specifically aimed at measuring ambient dioxin levels both in theincinerator room and on the facility grounds.
Incinerator room air sampling was performed at a location in thesouthwest corner of the incinerator high bay area as shown in Figure 16.Sampling was performed during these time periods; for an almost 12-hour Lr\
period on September 4, 1985, encompassing the blank burn test; for an almost • ~55-nour period beginning September 16 and ending September 19 while ounsuccessful attempts were being made to conduct the full test burns; and fop-sa 40-hour period beginning September 20 and ending September 22, encompass!nothe two full-burn tests. . °
All sampling was performed by pulling incinerator room air through anXAD-2 resin cartridge. A standard MM5 train glass resin cartridge containing17g of resin was used for the September 4 sampling. For the sampling periodsbeginning September 16 and September 20, the resin cartridge consisted of aglass drying tube filled with a comparable amount of XAD-2 and held in placewith glass wool plugs. Sampling on September 4 and the period beginningSeptember 16 was at 4 L/min. Sampling for the period beginning September 20was at 20 L/min.
After sampling, the resin was extracted and extracts concentrated, runthrough a cleanup procedure, and analyzed for 2,3.7,8-TCOO by GC/MS by thesane procedures noted in Section 3.2 for f lue gas MM5 train samples.
Ambient air sampling was performed during about the same 40-hour periodbeginning September 20 that the final Incinerator room and sampling effortoccurred. This period encompassed the full test burn period. The ambientalp sampling methodology used was In accordance with that developed by theNew York State Department of Health and demonstrated In the BinghamptonOffice Building. In this method, ambient air is pulled through a two-stagesampling device consisting of a 47-mm glass fiber filter and a glass resincartridge charged with 8g of silica gel. Preassembled devices, prespikedwith dioxin surrogates, were obtained from Battelle-Columbus Laboratories foruse. Samplers were placed at two locations near the CRF, Illustrated in
68
ih«w« it—* «r ••
Flyure 16. Ambient sampler location In the Incinerator high bay area.
000154
Figure 17 . Sanpl ing was performed at 20 L/mi n for the durat ion of thesampling period.
After samp l ing , tie preassert) led devices we^ returned to Sa t te l l e for?C30 and ?C3F a n a l y s i s . The analyt ical procedure 'Jsed was a Ba t te l l amodi f ica t ion to tne £PA Region VII protocol, "Determination of 2 ,3 ,7 .3 -T :GOin Soi l , " ( 1 9 8 3 ) . In tn is method the f i l ter and sor5ent resin are ext ractedwitn benzene and the ext rac ts concentrated, run through severa l extractcleanup s teps , tnen analyzed for tetra-CDD, penta-C3D, hexa-CDO, hepta-CDO,octa-CDD, tetra-CDF, penta-CDF, hexa-CDF, octa-CDF, 2,3,7,8-TCDD, and2,3,7,8-TCUF Oy HRGC/HRMS.
Results from the incinerator room (high bay area) samples are shown inTable 24. As noted in the table, measured high bay ambient air 2,3,7,8-TCOOlevels were nondetectable during the blank burn and full test burn periods.However, during the final test preparation period (September 16 through 19 ) ,the quantity of 2,3,7,8-TCDO detected in the extract sample normalized by thevolume of air sampled would correspond to an ambient concentration of ^n9.2 ng/m3. ^
This result is not surprising in retrospect. The final days prior to '~~successful performance of the full burns were a period of intense activity in 0the incinerator room. During this time a few minor waste spills and leaks ooccurred as waste feed systems problems were being attacked. Although these Qwere rapidly cleaned up, it is likely that some contaminated fugitive dustpanicles existed in the ambient air for some periods of time. These are themost likely source of the dioxin accumuTated in the room air samples. Ofcourse, all personnel working in the high bay area during this time were inLevel B protective clothing, complete with respirator and face shields, sodirect worker exposure would not have occurred.
Results from the outside ambient air samples obtained during the fulltest burn period are summarized in Table 25. As shown in the table, notetra- (including 2,3,7,8-tetra), penta-, or hexa-COOs or CUFs were found atlevels above detection limits in any of the ambient air samples or blanksamples analyzed. Total hepta-CDO was found in both ambient air samplecartridges, but comparable levels were found in the blank cartridges. Levelsof total octa-CDO, hepta-CDF, and octa-CDF in the sample resin cartridge atlocation 2, the one furthest from the incinerator stack, were detected, butagain comparable levels were found in the blank cartridges.
The only results for which sample levels were possibly significantlygreater than blank levels were total octa-CDD and hepta- and octa-CDF forsampling location 1 (just below the Incinerator's stack). The data inTable 25 suggest that the ambient air at this location may have contained anaverage concentration of about 50-pg/n»3 total octa-CDO, (blank cartridgevalue taken to correspond to 40 pg/m3), 0.2 pg/m3 of total hepta-CDF (blankvalue taken to correspond to 0.35 pg/m-), and l-pg/rn^ total octa-CDF (blankcartridge value taken to be zero, all blanks were nondetectable).
70
Figure 17. Outdoor ambient sampler locations during tne Vertac waste burns.
71
TABLE 21. INCINERATOR ROOM AMBIENT AIR SAMPLING RESULTS
Sampl ing Volume 2 ,3 ,7 ,8 -TCUOStar'; data:time rate saroleo concentrat ion
'ime penod to stop data:fime (L/min) (^3) (ng /m^)
B l a n k b u r n
F i n a l testprepara t ions
F u l l testburns
9/4/85:0950 to9/4/85:2135
9/16/85:0740 to9/19/85:1425
9/20/85:1700 to9/22/85:0250
4
4
20
2.32
18.9
40.6
<1.3a
9.2
^^
3< = Numbers denote less than minimum detection limit of theanalysis methodology for the appropriate sample analyzed.
TABLE 25. OUTSIDE AMBIENT AIR SAMPLING RESULTS
Laboratorymethodblank
Parameter (pg/ir3)
Blankfilter/resina(pg/m3)
Blank .filter/res^(pg/m3)
Samplinglocation ih
(P9/"'3)
Samplinglocation 2b
(pg/m3)
2,3,7,8-TCDOTotal tetra-COOTotal penta-CDOTotal hexa-COOTotal nepta-CDDTotal octa-CDD
2,3,7,8-TCDFTotal tetra-CDFTotal penta-COFTotal hexa-CDFTotal hepta-COFTotal octa-CDF
<0.047<0.047<0.10<0.044<0.86<1.7
<0.053<0.053<0.040<0.027<0.86<1.7
<1.0<1.0<1.1<0.719.2
41
<0.89<0.89<0.44<0.58<1.5<6.3
<1.1<1.1<0.28<0.174.5
40
<0.20<0.20<0.067<0.100.35
<0.38
<0.95<0.95<0.58<0.439.9
90
<0.28<0.28<0.24<0.26
0.570.98
<0.77<0.77<0.20<0.184.5
41
<0.20<0.20<0.11<0.0720.27
<0.21
aTwo preassembled sainpling devices were submitted as trip blanks.bSee Figure 7-2.
72
The total measured COD plus CDF from the above, thus was about 50 pq/m3.The preliminary risk assessment included in the test protocol document (5)for these tests noted that current data suggest tnat an increased lifetimecancer r isk of 1 in Id4 would be associated with continuous lifetime exposureto ambient levels of 2,3,7,8-TCDD of 10.3 to 31.5 pg/m3. if all isomers ofall PCDDs and PCOFs analyzed were considered to be as carcinogenic as2,3,7,8-TCOD (a very conservat ive assumption), then a 50-pg/m3 total ambientlevel would be associated with increased lifetime risk from continuouslifetime exposure of between 1.6 in 10^ ana 5 in 104.
REFERENCES
5. "Protocol for an Incineration Study of 2.4,5-T Stnibottoms with TCDO 03Contamination," prepared by Versar, Inc., Southern Operations for inEPA/HWERL, Combustion Research Facility. July 1985. _.
000
73
TECHNICAL REPORT DATAfPfeesi read .'MS-'ucnons on l/ic rtftf.t tefort comnlfnnt!
3. alC.PlENT-S *CS£SS1C»» NO.
4. TITLE *^3 S'^BTlTLt
^ - ' l o t - S c a l e I n c i n e r a t i o n Tsst B u r n or" T C S D - C c n t a m l n a t e cT n c r t l o r o p h e n o i P roauc t ion was ie B. PERFORMING ORGANIZATION CCOE
7. AU'MCBiS) _Ross, R . ^ . , Backhouse, T .H . , /ocque, R . N . , Lee, J . W . ,waterlana, L.R.
1 . PERFORMING CRGANl;ATIO^ HEPC«' "•O
9. ^ E B F O R M I N a O X O A N I Z A T I O N NAMf ANO AOOHESSAcurex Corporation485 Clyde AvenueMountain View, CA 94039
10. f R f a Q H A M E L E M E N T NO.
1 1 . CCNTBACT/GBANT NO.
Contract 68-03-3267
13. SrONSOHING AGENCY NAMt AND AOOKISS
Hazardous Waste Engineering Research LaboratoryOffice of Research and DevelopmentU.S. Environmental Protection AgencyCincinnati. OH 45268
13, TY»e Qf fWOHT ANO »tf<100 COVlatO
14.SPONSOHINQ AGENCY COOl
EPA/600/12
9. SU^t.£MENTAflY NOTIS 00
-0-H. AgSTHACT
A series of three tests directed at evaluating the incinerabnity of the toluenestitlbottonis waste from trichlorophenol production previously generated by theVertac Chemical Company were performed in the Combustion Research Facility (CRF)rotary kiln incineration system. This waste contained 37 ppm 2,3,7,8-TCDD as itsprincipal organic hazardous constituent ( P O H C ) . Flue gas 2,3,7,8-TCDO levels were 'lessthan detectable at all locations sampled. Corresponding incinerator destruction andremoval efficiencies (DREs) were greater than 9 9 . 9 9 9 7 percent, based on individualsampling train analyses. By analyzing combined extracts from four simultaneoussampling trains, it was concluded that 2,3,7,8-TCDD ORE was indeed greater than9 9 . 9 9 9 9 percent. These results suggest that incineration of the Vertac waste iscapable of achieving the required ORE and should be considered a treatment optionfor this waste.
7. K«Y WOHOS ANO OOCUMINT ANALYSIS
b.lO«NT1FieHS/0>«N 8NOtO TIBMS C. COSATI Fuld/C/ou?
11G
H. OlSTBIBUTlON STATEMCNT
Release to public1«. 11CUKITY CLASS iriuiKlpwvi
UNCLASSIFIED2 1 . N O . O F PAGES
ifl. SSCUHITY CLASS tTlmpfsv/
UNCLASSIFIEDCPA ffrm 2220.1 <».73»
^P^/^/Z-t^/fZ!
3eceToer 1986
" v ^ m c "
PILOT-SCALE INCINERATION TEST BURN OFTCDD-CONTAMINATED TRICHLOROPHENOL PRODUCTION WASTE
Project Summary
By
R. W. Ross, II, T. H. Backhouse,R. H. Vocque, J. W. Lee, and L. R. Waterland
Acyrex CorporationEnvironmental Systems DivisionCombustion Research FacilityJefferson. Arkansas 72079
EPA Contract 68-03-3267Work Assignment 0-2
EPA Project Officer: R. A. CarnesHazardous Waste Engineering Research Laboratory
Combustion Research FacilityJefferson, Arkansas 72079
FOP
HAZARDOUS WASTE ENGINEERING RESEARCH LABORATORYU . S . ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
0
v0
0
00
1. INTRODUCTION
A primary function of the Environmental Protection Agency's (EPA)Combustion Research Facil i ty (CRF) is to perform incineration testing oftrouolesome hazardous wastes to support decis ions regarding whetherincineration is a proper waste treatment and disposal option. One c l ass ofsuch wastes are tnose contaminated with 2,3,7,3-tetrach' lorodibenzo-p-dioxi n(2,3,7,3-TC3D or d iox in) .
An example of a well-documented, highly dioxin-contaninated waste is thetoluene s t i 1 1 bottoms from trichlorophenol production previously generated andcurrently being stored, pending a decision regarding appropriate treatmentand disposal, at the Vertac Chemical Company in Jacksonville, Arkansas. Thegenerator is currently considering onsite incineration in a mobileincinerator system for disposal of this waste and wishes to have a permit fora trial burn. The primary objective of the tests reported herein was toevaluate the indnerability of the Vertac toluene sti 1 1 bottoms waste bydetermining whether 99.9999 percent ORE could be achieved as required bycurrent regulations. Results of these incineration tests could in turn beused to support any subsequent permit decision.
All tests were performed in the CRF rotary kiln incineration system. 'r-
The test program consisted of a-total of four trial burns performed in ^°September 1985. These trial burns consisted of the following: ^~
0• A blank burn with the Incinerator fired with auxiliary fuel Q
(propane) to establish background emission levels of pollutantsof concern —
• A mini burn of short duration (4 hours) with waste fired at nominally17 kg/hr (38 Ib/hr) to demonstrate the ability to feed andincinerate the waste and to gain experience with the samplingprotocols specified
• Two full waste test burns of nominally 10-hour duration with thewaste fired at about 10 and 18 kg/hr (22 and 39 Ib/hr) tospecifically address the test objectives
2. FACILITY DESCRIPTION, WASTE CHARACTERIZATION. AND SYSTEM OPERATION
The rotary kiln incineration system at the CRF consists of a rotary kilnprimary combustion chamber, a fired afterburner, and a primary air pollutioncontrol system consisting of a venturt scrubber, wetted elbow, and packedtower scrubber. In addition, a backup air pollution control system (APCO)consisting of a carbon-bed absorber and a HEPA filter 1s in place. Theprimary APCD might be considered reflective of what might exist in an actualcommercial or industrial Incinerator. The backup system Is in place toensure organic pollutant and particulate emissions to the atmosphere arenegligible. A schematic of the system is given In Figure 1.
IrdnsferDuel
Reclrculdtton Huctrculallon IHoMtlown lllow.lowr'WHP lank fink Id.ik
Mo. I Nu. <'
Figure 1. Simplified rotary kiln system schematic.
0 0 0 1 6 2
II) fan
111 i l l d i l l
Pro|)«ne —"•-M^ Afterburner
U
S d O l l d C /
l*^*-!*-"* SCWI;!
(^y-- » (IlL'lllllJl
StiWL'l
For these tests, waste was introduced at the feed face through the frontface lance with a diaphragm-type pump, while auxiliary fuel (propane) wasfired through a burner located at the transfer duct end of the Hi In. Theafterburner was also fired with auxiliary fuel.
Taole 1 summarizes the nominal incinerator operating conditions for eachof the tests performed. For all four, propane was fired in the ciln and theafterburner to maintain the kiln at about 1800°F and the afterburner at about2000°F. This corresponded to heat inputs of about 250 to 350 kW (0.9 to1.2 x 106 Btu/hr) in the kiln and about 470 to 560 kW (1.6 to 1.9 x106 Btu/hr) in the afterburner for a 1 1 four tests.
The amount of waste fed into the kiln was monitored by recording thechanges in the waste container weight reading. The feedrates fluctuated overa wide range, with mean rates of 17 kg/hr (38 Ib/hr) on September 9; 10 kg/hr(22 Ib/hr) on September 20; and at 18 kg/hr (39 Ib/hr) on September 21,1985.
System residence times were calculated based on volumetric flowratemeasurements using a helium tracer system and the assumption that the kiln ^and afterburner chamber temperatures were isothermal and equal to the single •?—point measurement noted in Table 1. The calculated residence time in the Qkiln main chamber was 5.7 sec for the blank burn, 5.3 sec for the miniburn,and 4.9 and 6.0 sec for the two stillbottoms waste full burns. Residencetimes in the afterburner were 2.1, 1.9, 1.8, and 2.3 sec for the respective °tests.
The generic composition of the toluene still bottoms waste based onprevious data developed by the Vertac Chemical Company, and the physicalcharacteristics of the waste based on analysis performed on a sample of thewaste at the CRF are given In Table 2. The waste was also analyzed for theorganic and trace element priority pollutants. Results of these analyses aregiven in Table 3. Specific analyses for the Principal Organic HazardousConstituent (POHC) in the waste. 2,3,7,8-TCDO, showed that it contained37 ppm of this compound.
Significant problems were experienced with attaining and maintainingwaste feed throughout the test program. Specific problems included continuedfeed lance clogging, due to carbon buildup (coking of the waste material), inthe lance, with pump check valve seal failure, and with the ability to pumpwaste. The feed lance clogging problem was solved by cofeeding water withthe waste so that when the lance clogged it would heat and vaporize thewater, thereby, clearing the clog. Feed line clogging and check valve sealsticking were temporarily solved by cleaning all feed line components withsolvent (toluene). However, in retrospect the choice of a diaphragm pump forthis waste was Inappropriate. The waste was waxy and very viscous at roomtemperature. Only at about 95°C (200°F) would it flow sufficiently to beconsidered pumpable. Hot water heating coils were immersed in the waste forthese tests, however, pumping problems persisted. Perhaps a pump of anotherdesign, such as a progressive cavity pump, would have provided betterservice.
TABLE 1. INCINERATOR SYSTEM OPERATING CONDITIONS
Kiln opTttlon
fTooJiM hnt Infxil. kM(10» •tu/kr)
MJif fwdrtf. kg/hr(Ib/hr)
U«tf hWt llfKlt. kU
(lO* HtH/hr)
txll OJS tonpTltura. •CCf»
MrlMl ciil—iK* t<— re*
A(terburn*r ODT«tlon
froa*— hut InfMt. W(10» (tv/kr)
Eilt |«l fpT«tur«. *CmMrln«l r*tl«*iK* (1— sec*
WCtt apTitlon
Syst— uJtT —kiip r*ta. I/Bin1<4»)
Sy»t— kloikMl r«f, (./•In(W»
ScrubbT liquor pM
Venturl prtour* 4rop. kr«(In. NC)
Venturl ult u*(—p«r*tur«, •Ccnr«cli«d tJMf pfltur* drop. kp«(til. UC)
pJckil to—r wit g*<lewr*tur*, •Ccn
•Hctl^nc* tl—l lurd an •aluflrl
BJCkuround(»/«/a5
(N50 la 19
lltng*
Z60 to »0(O.t to 1.0)
470 to &M(l.t ta 1.7)
I? to 17(1.2 ta 4.4)
••• to «.)(l.a to Z.4)
8.4 to B.S
10.7 to I0.«(41 f 44)
0,}i to O.SO( 1 . 4 to 2.0)
Ic flom c*lculilfd ulinq
humi140)
A»T«««
wa(O.»i»
00
00
ISO(I'M)
&.7
4110(l.*4)
1120(M40)
Z.I
IS(4.0)
9.2(».Z)
«.s
10.7
(«*»
7»(174)
0.44(!.'»»
711(1 '2»
HInlhurn(9/1/8S
094& to tW
XJng* i
IBO to ZW(0.6 to 1.0)
a ta n(18 to SO)
)7 to 101(0.11 to 0.3S)
440 ta WO(I.S to 1 .7 )
10 to 19(Z.7 to 4.»)
4.9 to a.l( 1 . 1 to 2.2)
8.0 to 8.7
a.Z la 10.0(33 to 40)
n.3u 10 0.50(I.Z to 2.0)
Lh* helliM lr«cc
00
»
kv*r«ge
IM(0.77)
1 7(M»
77(O.Z6)
MO(IB20)
&.3
470(!.»»
1120(20SO)
1.9
IS(1.9)
7.21.9
••2
9.5(!»»
UU(176)
0.401.6
78( 1 7 1 )
ir <yitc
0 1
fint rull(1/20/Bi
1010 to 22
Hinge
120 to 440(I.I (0 1 . & )
0 ta 2S(0 to •>*)
0 ta 1 1 4(0 ta 0.19)
&00 ta S90( 1 . 7 ta 2.0)
9.S ta 30(2.S to 7.8)
1.4 to 11(0.1 ta 1.4)
•.0 ta 8.6
7.S ta 10.0(U to 40)
0.47 ta 1.3(1 .9 to &.?»
llJt*.
6 4
burn
-10)
A«cr*i)C
3B<( 1 . 3 »
10W
44(0.1S)
980(1800)
4.9
&60(1.9)
1 1 1 0(2010)
1.1
?!(S.4)
8.7(2.1)
8.2
8.6(IS)
HI(I'll)
1.0( 4 . 1 )
tUI( 1 7 6 )
Second lull liO/.'l/il'i
I/IS In / I I
RiOiJI!
Ztll to 3"il)( 1 . 0 to 1 . ? )
2.1 to <ll(i lo »'»
1 2 to 1>10(0.04 tu 1 1 . 6 1 1 )
WO tu i>t>lj( 1 . 7 to 1 . 1 )
6.H ta ? 1(1 .8 to 6.0)
4.& III 1 1( 1 . 2 ta 2.8)
6.8 tu 8.1
7.0 ta 1.1(28 ta If)
U.IS ta 1 . 1( 1 . 4 10 •1 .4 )
urn
"1
Aver^Jf
Jlil( 1 . 1 )
IH(M)
1X1(U.;/)
y«)
( IHIII)
6 . 1 1
S/11( 1 . H )
1 1 1 0(/nin)
if. I
Ih
( 4 . 1 )
H.I
( . • . 1 1
S.2
B.S
( 1 4 >
H/
( 1 1 1 1 1 )
0 . 1 1 S
( 1 . 4 )
ill( 1 / H )
TABLE 2. STILLBOTTOMS WASTE GENERIC COMPOSITIONAND PHYSICAL CHARACTERISTICS
CompoundConcentration
(percent)
Metnanol 1Toluene 3Oichlorobenzenes 1.5Tricniorobenzenes 1.52,4,5-trichloroanlsole 56Na-trichlorophenol 7Oichloromethoxybenzene 162,4,5-T, Na salt 7
Parameter Value(Percent)
density, g/mlon drying, percent
BulkLossAshHeating MJ/kg
(Btu/lb)value,
1.3713.25.1
16.11(6945)
3. SAMPLING AND ANALYSIS PROTOCOL
The combustion gas generated during each test was monitored at variouslocations in the system for CO, COg Og, NOx, total hydrocarbon (THC), HC1,particulate, and trace semlvolatile organic compounds, most importantly2,3,7,8-TCDO. In addition, grab samples were obtained of the waste feed, thescrubber system blowdown liquid, and the ash collected in the ash pit duringthe tests. Ambient air sampling, both in the high bay incinerator room andin the outside vicinity of the CRF was also performed. Figure 2 summarizesthe sampling locations and types of samples obtained.
Waste samples were analyzed for 2,3,7,8-TCDO by dilution, cleanup, andhigh resolution gas chromatography/low resolution mass spectrometry(HRGC/LRMS); for the halogenated volatile organic priority pollutants bydilution, purge and trap SC/electlon capture detector (ECD); for thesemi volatile organic priority pollutants by dilution, cleanup, and HRGC/LRMSin accordance with Method 8270; and for the priority pollutant trace elementsby add digestion and atomic absoration techniques.
K 1 1 n ash and blowdown water samples were analyzed for polychlorinateddibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCOFs) of
TABLE 3. COMPOSITION OF THE STILLBOTTOMS WASTE
Conesntr i t -on^ Oeteet ton 1iim:Comoonent 'PC", "rt! ;3Dn, >rt'
V o l a t i l e orsani ; o n o r - ^ y s o i l J t a n t s
Mctny lene ;n1onde1,1-dic ' i loroetnylene1,1-dicn'locoetianet- l ,2-dici)oroethy1eneChloroform1,2-dlcnloroetnanel.l.l-tr-icnioroethaneCarbon tetrachlorldcBromocfi 1oroncthane1,2-<11 en 1 oropropy 1 enec-l,3-d<eh1oroppopyleneTricmoroethy1eneBenzene1,1,2-tMchloroethanc3rwnfarwTetrachloroethylene * tetpachloroethaneChloroBenzeneToluene
Sem1vo1atne organic pploplty pollutants
1.2-<11ch1oroben2ene1,2 ,*-ti-l chl orobenzencA11 otner base/neutral senlvolatl le
priority pollutantsl,2-»d1cn1oropheno14-cn1oro-3-metnylphenol2.4,6-tr-lehlorophenol2,4-dlnltrophcnol4-nltropheno'l2-flrtHyl-4,6-dlnitpophcnolPentachlorophenolA11 other add sem-1 vola t i le
pollutants
Tpace Elements
Antimony, SbArsenic. AsBeryl l ium. BeCadmtuffl, UQiroB'tuw, CrCopper, CuLead, PbKTeyry, HgNickel, N1Selenium, SeStiw. AgTh»niu«. nZinc, An
159,000 ~
3.410
priority
277NONO10•c•cfOw»
NO(C»N0NONOTONO
2,690
W
. 159NONONONON0NO»
CNONONONONO4NON0NONONONO
^^
4212708442427042844242
UO42708442
^^
500
.-500 '300300500500500100
213111111111
10
*NO denotes not detected at tne detection l imi t noted.
[ ! ]
Test SampleParameter
COg
QZsensor
CO
NO,
HC1
THC- detector
Sem1volatile 3,4,6organ!csincluding2.3,7,8-TCDO
Waste
Kiln ash
burn series
Scrubberblowdown
burn series
points Methodology duration
3,4,8 NDIR Continuous
3.4,8
3.4,8
(7 dscm)(250 dscf)
>«ur,*1 Ift
1!1
3,4
6
6,7
1
2
5
1i])
,8
Cotorimetric Continuous
Flame ionization Continuousa
Grab
Grab 8 composites 8
Grab 8 composites
Aft»r*Mn*«r
4 1 ' 1 1 kl ' 1
Zirconium oxide Continuous
NDIR Continuous — ^
Cheniluminescence Continuous
,8 W5
™
10 hours
| *f*^r-4 tCr\.«b«r'n .»..<1 —
1 •ICI— [ I :t-WI [- -. ^». h( itn—»f ] ] ] •• •-*»• 1
after
after
1
entire
entire
< •'"" i • '\^ i 5.ii
NO. Ofsamples
r--^0
000
2 at test pt 32 at test pt 44 at test pt 62 at test pt 8
3
> 8
^he two test points were monitored by one instrument on a 5-mintime-sharing basis.
Figure 2. Summary of the general sampling protocol
chlorine substitution 4 through 8, and for 2,3,7,8-TC30 by benzeneextraction, extract concentration and cleanup, and HRGC/HRMS.
Blowdown water samples were also analyzed for the halogenated volati leorganic priority pollutants by purge and trap GC/ECD; for the semi vo la t i l e 'organic priority pollutants by benzene extraction, extract concentration, andHRGC/LRMS; and for the priority pollutant trace elements by atomicabsorption.
Modified Method 5 (MM5) train samples were benzene extracted, extractsfor all train components combined, concentrated, and subjected to extractcleanup procedures. These extracts were then analyzed for 2,3,7,8-TCOO byHRGC/LRMS. In addition, extracts for the four simultaneous MM5 trainsoperated downstream of the scrubber system for the two full-burn tests werecombined and analyzed for 2,3,7,8-TCDD. The sample from this area of thesystem, the "virtual stack" or "E-duct" are very important since these datawill be used to design future systems. 00
v04. TEST RESULTS i—
Levels of O^, COg, CO, and N0^ in the flue gas at the afterburner exit °and in the stack for the four tests performed are summarized 1n Table 4. As °shown, all tests were performed at high excess a1r; flue gas 0^ was in the 010 to 17 percent range in the afterburner exit and in the 13 to 17 percentrange in the stack. CO emissions were always low, <10 ppm, as were NOxlevels, <30 ppm. The missing data noted In Table 4 illustrates anotherproblem experienced during the tests, that of continuing continuous monitorfailure. Although the CRF has two complete monitoring systems (0^, CO^, CO,and NO'x), during these tests only one of each set of Instruments was workingand even some of these working Instruments would periodically fail.
Table 4 also noted the HC1 emission rates for those tests for whichthese were measured. For the nrlniburn, the HC1 emission rate was 0.45 kg/hras measured by the continuous HC1 monitor at the E-duct; for the September 20full burn the HC1 emission rate was 0.25 kg/hr as measured both by the HC1monitor and by the MM5 trains operated at the E-duct. Both of these are lessthan the CRF permit level of 0.5 kg/hr.
Table 5 summarizes the particulate and 2,3.7,8-TCDO emission levelsmeasured at various locations in the Incinerator system for each of thetests. As shown in the table, particulate levels at both the kiln andafterburner exit were quite low during the background burn with propane fuelalone, as expected. Flue gas paniculate levels for the tests with wastefeed were highly variable and ranged from several to several hundred mg/dscn.Particulate levels at the virtual stack were indicated to be as high as340 mg/dscra for one test. Due to technical factors, and since the 0^ monitorat this location was not operating properly at the time of the test, accuratefigures, corrected to 7 percent 0^, cannot be derived from the raw data.Since results are uncertain, further work on measurement of particulateemissions from dioxin-contaminated waste 1s needed.
TABLE 4. EMISSION MONITOR AND 4C1 EMISSION RATE DATA
Background First Secondburn Mini burn full burn full burn
Parameters 9 /4 /85 9 /9 /85 9 /20/85 9 / 2 1 / 3 5
Afterburner exi t ;
Og (percent)CO^ (percent)CO (ppm)NO)( (ppm)
E-duct:
HC1 (kg/hr)ContinuousAnalyzerMM5 train
Stack:
O? (percent)COg (percent)CO (ppm)NOx (ppffl)
158
30
177
<10
127
<1020
0.45
183
30
104
<1010
0.25
0.25
174
<1020
138
•- Denotes monitor not operating or measurement not made
Paniculate emissions at the stack system (after the High EfficiencyPaniculate Filter) were also indicated as being much higher thananticipated. The values are 5 to 15 times higher than design values, and aretherefore suspect. Further testing is needed to determine the nature andsource of the paniculate. If they are indeed as high as indicated.
Flue gas levels of 2,3.7.8-TCDD were less than method detection limitsat all locations for all tests. These levels correspond to the ORE valuesnoted In Table 5 for the tests with waste feed. Two sets of ORE values arenoted in the table for the E-duct and stack locations. These correspond totwo different measures of flue gas flowrate. One of these was based on ahelium tracer injection system; the other was based on the MM5 train velocitymeasurements. The data in Table 5 suggest that 2,3,7,8-TCDO ORE wasgenerally greater than 99.9997 percent in the virtual stack which wouldlikely correspond to the stack of an actual hazardous waste incinerator.
TABLE 5. PARTICULATE AND 2,3,5.8-7C30 EMISSIONS AND2,3,7,3-TCDO ORE
:ite <na "is; 'oci:'on
3iCi;rBuna Sun 5 /< /35
min txit: 'r»'n ITrim 2
Afttroumtr Tr*in I(lit: Tr*in 2
E-duCt: TOB trttnB«t;aB tr«lnL*^t tr«1nRlqnt triln
Stick: East trimSoutn tr»ln
Writ Burn 9/9/85
Klin txit: Tflln 1Trtin 2
AfttfBurn»r Train 1till; Train 2
Fall ium 9/ZO/85
Kiln •x1t: Triln ITr*in 2A«T*9«
*frrttufn«r Triln 1till: Tr»)n 2
E*4uct: Too trill)Boctaa trilnLtfl tr»fnBiyit (r«1nA««r*g«
Sfcx: EJSt trilnSoutA trilnA»«r*g«
Full aurn 9/?1/85
tlln *x1t: Tr»fn 1Tr»ln 2
AfttrflurnT Triln I•x<t: Tr«ln 2
Avrif
E-4uct: Top tr»<Blotf trilnL«ft tr»fnBiyit tr«(n
SUM: Eilt tr«)nSouth trilnAvriq*
Panculit
'fiq/aialas -MiSJrMI
0.230.50
0.833.*
.J>
.-!>--6.J>
2.33.*
K3175
S3S2.030
2.71l.««2.09
371t
WW291Z51343
38.4U.O47.2
7531,940
1S4l9»17S
<0.1S2.3
10.8<0.13
72.6208140
t willloni
','iuj/asmC3rr»c;M ;31 ;er;«nt O;1
1.97.3
a.i1.4
<13<ll
132378ZS5
\
',3.7.3-'C30wnssians•.ig/asca)
<Q.95<0.36
<1.7<0.43
<0.1B<0.24<0.3l<0.3l
<0.21<0.10
<0.74<1.4
<0.55<0.17
<3.a<1.3
<0.43<0.5l<2.5<0.5i
<2.3<l.S
<8.4<21
<3.»<2.8
<l.i<2.0<2.2<0.7<
<1.5<l.i
2.3.'.3-''C30 311
3lSM initl (.nil ftctr
>99.WW>99.99991
>99.9984>»9.998<
>99.99992>99.99998
>99.99903>99.999<7
>99.99982>99.99979>99.99896>99.99977
>99.99907>99.9994S
>99.99964>99.99988
>99.9995«>99.999<9
>99.999«9>99.99W>99.99»64>99.99988
>99.99»7S>W,9W3
!E •';»'';tnt)
iiseaan "Jtgtt
«».oc' ty
>99.99987>99.99985>99.99925>99.99983
>99.99916>99.99951
>99.99974>99.99973299.99970>99.999897
>W.iW7«>W.9W73
*0; •—tT not functioning propwiy. Ftgurn, •n«n ii»»fl, in *«t1wt«i.^ fllttri —r* us*d In tn« E-4uct tr«1n» for tn1t tttt.'EilOnct of a »fgnlf1e*Bt s—llig tr»ln 1*«k •«i 31ico»«»^d «ft»r » aUng w«s CiMpItt*. Oltl—r« coniiMnd in»*I1a for p«rt1cul4f ••isumwrtl.
10
Method detection l imits did not al low unaraoiguiously es tab l i sh ing thatgreater than 99.9999 percent ORE was achieved either at tne v i r tual stack orat the system stack. Therefore, fe extracts from the four ^M5 t ra insoperated at the virtual s tack for tne two full-Sun tes ts •^e1'0 conoined andreanalyzed in an attempt to ach ieve Setter detection l imits. C a l c u l a t e d2,3,7,8-TCDD levels for the vir tual s tacK, and corresponding 2 , 3 , 7 , 8 - T C D DDREs based on the combined extract analyses for the second full 3urn(9 /21 /36 ) are given in ^able 6. The data for the second full burn clearlyshow that greater than 99.9999 percent ORE was achieved. The ext racts forthe first full burn were spiked with an order of magnitude higher level ofrecovery standard than appropriate by the of fst te laboratory which originallyanalyzed the individual train extracts. As a consequence, method detectionlimits corresponding to ng/dscm of flue gas were not better than for theindividual train analysis data as summarized 1 n Table 5.
The kiln ash and the scrubber- blowdown water from this entire testseries was analyzed for PCDOs and PCDF of chlorine substitution 4 through 8.The kiln ash samples were devoid of PCDDs and PCOF to detection limitsranging from 3 to 40 ppt, as shown in Table 7. Similarly, the data in 0Table 8 show that scrubber blowdown samples were devoid of all PCODs and QPCDFs except octa-COOs which were present at 0.07 ppt. This is notsurprising since octa-CDOs are relatively common in environmental samples.
r--
o
The scrubber blowdown was also analyzed for the organic and traceelement priority pollutants. Results are summarized in Table 9. As shown,no organic priority pollutant was present in the blowdown at levels greaterthan 10 ppb. In addition, none of the trace elements were present atconcentrations which would cause the blowdown water to be considered EP(Extraction Procedure) toxic. Based on all analytical data, the blowdownwould not be considered a hazardous waste.
5. CONCLUSIONS
A series of incineration experiments was performed with the VertacChemical Company's toluene still bottoms waste from trichlorophenolproduction. This waste is one of the more well known of thedioxin-contaminated wastes presently in existence. Samples of the wastetested in this study contained an average of 37 pom 2,3,7,8-TCDO (37 ug/g).
Three incineration tests were performed during September 1985. All wereperformed in the CRF rotary kiln incineration system with waste feedratenonnnany 20 kg/hr.
With regard to the principal objectives of these tests, the followingcan be concluded:
• 2,3,7,8-TCOO ORE based on the combined extracts from the four MM5trains at the virtual stack was greater than 99.99999 percent forone test. For the other test method detection limits preventedquantitating that better than 99.9998 percent ORE was achieved.
11
TABLE 6 . 2,3,7,3-TCOO EMISSIONS AND 3RE BASED ON COMBINED E-OUCTTRAIN EXTRACTS
2,3,7,8-TCDD ORE
rest date
2.3.7,8-TCDOemissions Based on Based on(ng/dscm) helium tracer flue gas velocity
Full burn 9/21/86 <0.066 >99.999989 > 9 9 . 9 9 9 9 9 1
TABLE 7. LEVELS OF PCDD AND PCDF IN KILN ASH SAMPLES
Concentration3 (ppt^
Analyte
2,3,7,8-TCDDTCDDs-CDDPenta-CDDsHexa-CCDsriepta-CDOsOcta-CDOs
2.3,7,8-TCOFTCDFsPenta-CDFsHexa-CDFsHepta-CDFsOcta-CDFs
Sample 1
(13)(13)(28)(7.4)(14)(44)
(7.0)(7.0)(11)(4.6)(12)(33)
Sample 2
(10)(10)(6.5)(4.5)(6.3)(18)
(16)(16)(2 .7)(2.8)(6.2)(21)
Sample 3 Sa
(5.6)(5.6)(4.2) (16)(5.0) (37)(3.4) (8.4)(15) 235
(7.1) (10)(7.1) (10)(1.7) (6.4)(3.1) (7.4)(3.4) (8.4)(15) (40)
unple 4
28)2 8 ) -
lumbers In parentheses denote analyte not detected tothe detection limit noted In parentheses.
b! ppt « 1 pg/g.
12
TABLE 8. PRIORITY POLLUTANT COMPOSITION OF THE SCRUBBESSLOWDOWN WATES
Anal.yte
2,3,7,8-TCDDTCODs-CDOPenta-CDOsHexa-CCDsHepta-CDOsOcta-CDOs
2,3.7,8-TCDFTCDFsPenta-CDFsHexa-CDFsHepta-COFsOcta-CDFs
Sample 1
(0.005)(0.06)(0.04)(0.03)(0.02)0.07
(0.02)(0.1)(0.02)(0.02)(0.1)(0 .1)
ConcentratK
Sample 1duplicate
(0.02)(0.08)(0.05)(0.04)(0.04)0.04
(0.01)(0.07)(0.02)(0.06)(0.02)(0.08)
ind ( p p ^ ) b
Sample 2
(0.02)(0.09)(0.04)(0.04)(0.03)0.07
(0.02)(0.1)(0.07)(0.06)(0.03)(0.06)
Sample 2dupl icate
(0.04)(0.09)(0.02)(0.03)(0.05)0.07
(0.02)(0.06)(0.03)(0.06)(0.03)(0.04)
lumbers- 1n parentheses denote analyte not detected tothe detection l imi t noted 1n parentheses.
b! ppt • 1 pg/ml.
13
TABLE 9 . PRIORITY POLLUTANT COMPOSITION OF THE SCRUBBER SLOWDOWN WATER
ConceComponent
V o l a t i l e orsani; sr-ionty s o l ' u t a n t s
Hetnylene cnlor- 'de1,1-dicnloroetnylene1,1-dichloroethanet-l,2-d1ch1oroethy1eneChloroform1,2-dlchloroethanel.l,l-tr1ch1oro€tnaneCarbon tetrachlondeBroreodi efti orometnane1,2-dlchloropropylenet-l,3-d1cn1oropropy 1 oneTricnioroethyleneBtnzcne1,1.2-trlcftloroethaneBroiao^onBTttrachlopoethylenc * tttrachlopotthaneChlorobenzene
( p p o
6.1
riV
'
NOwMONONOWNO«ffi«NONOWNOMlNO
"it 'onw t ) a
Detec t 'on1 lir ' t
( P P O , wt)
12.62.52.62.54.25.02.62.64.22.65.02.62.66.34.25.0
12.6
Seiii<vo1atn« organic priority pollutants
An 6<se/n<utral s«t1»o1atn» prioritypollutants
4-ch 1 oro-3-fliethyl phenol2,4,6-tr1emoropn»no12,4-d1n1troph«no14-nltrophenol2-wthyl -4,6-^1 n1 tpoph«no1P»ntacn1oroph«nolAn othtr add s«a1vo1at11e priority
pollutants
NO
NONO«NONONONO
5
50303050505010
EP toxidtyconcentration
(pow, wt) (ppiB, wt) limit (ppm)
Trace elements
Afftiaony, A6Ars»n1e, AsB«ry111w. B«CadMir, C4Cnrarlir, CrCopper. CuL««d, PbMTtury, H^Niclrl. N1Se1«n1u«, S«Silver. A .ThallluCT, 'nZinc, Zn
»1CNONONO4i»IbNO10
NONO«NO
21311111 •1111
10
.»
5—15...50.2..15..••
*W denotes not detected; duplicate samples analyzed.^ound in only one sample; not detected In the others.
14
• Accurate determination of particulate emissions at the virtual stackand system stack was not achieved. Further research is needed toobtain data on the amount, nature and source of paniculateemissions from these sources.
• HC1 emissions in the •/i-tual stack ranged t-om 0.2 to 0.45 <g/h~.These were below the CSF Part 3 limit of 0.5 kg/hr.
The above conclusions suggest that incineration should beconsidered a viable disposal method for this still bottoms waste, given thatappropriate safeguards are employed. The data in this study confirm thatan incinerator operating under proper conditions can achieve greater than99.9999 percent DRE for 2,3,7,8-TCDD, with HC1 emissions below the regulatorylimit.
15
PILOT-SCALE INCINERATION OF A DIOXIN-CONT.AINING MATERIAL
Larry R . Waterland, Robert W. R o s s , I I ,Thomas H. Backhouse, Ralph H. Vocque,
and Johannes W. LeeAcurex Corporation
Combustion Research FacilityJefferson, Arkansas 72079
Robert E. MournighanU.S. Environmental Protection Agpncy
Hazardous Waste Engineering Research LaboratoryCincinnati, Ohio 45268
Presented at the Fall Meeting, Western States Section,The Combustion Institute
University of ArizonaTuscon, Arizona
October 1986
ABSTRACT
A series of three tests directed at evaluating the incinerabi l i ty of thetoluene st i t lbot toms waste from trichlorophenol production previouslygenerated by the Vertac Chemical Company were performed in the CombustionResearch Facility (CRF) rotary kiln incineration system. This wastecontained 37 ppm 2,3,7,8-TCDD as its principal organic hazardous constituent(POHC). Flue gas 2,3,7,8-TCDD levels were less than detectable at alllocations sampled. Corresponding incinerator destruction and removalefficiencies (DREs) were greater than 99.9997 percent, based on individualsampling train analyses. By analyzing combined extracts from foursimultaneous sampling trains, it was concluded that 2,3,7,8-TCDD DRE wasindeed greater than 99.9999 percent. These results suggest that land-basedincineration of the Vertac waste is capable of achieving the required ORE and
IN'RODUCTION
One of the primary functions of the Environmental Protect ion A g e n c y ' s(EPA) Combustion Research Facility (CRF) is to perform incinerat ion test ingof troublesome hazardous wastes to support decisions regarding whetherincineration is a proper waste treatment and disposal option. One c lass ofsuch wastes is those contaminated with 2,3,7,8-tetrachlorodihenzo-p-dioxin(2,3,7,8-TCDO or d iox in) .
One wen-establ ished, highly dioxin-contaminated waste is the toluenestil1 bottoms from trichlorophenol production previously generated andcurrently being stored, until a decision regarding appropriate treatment anddisposal is reached, at the Vertac Chemical Company in Jacksonvi l le ,Arkansas. The generator is currently considering onsite incineration in amobile incinerator system as an avenue for disposal of this waste and wishesto have a permit for a trial burn issued. The primary objective of the testsreported herein is to evaluate the incinerability of the Vertac toluenesti ltbottoms waste by determining whether 99.9999 percent ORE could beachieved, as required by current regulations. Results of these incineration ^tests could, in turn, be used to support any subsequent permit decision, -r-
r--
0All tests were performed in the CRF rotary kiln incineration system. Q
The test program performed consisted of a total of four trial burns performedin September 1985. These trial burns consisted of the fol lowing: °
o A blank burn with the incinerator fired with auxi l iary fuel(propane) only to establish background emission levels of pollutantsof concern
• A miniburn of short duration (4 hours) with waste f ired at nominal ly17 kg/hr (38 Ib/hr) to demonstrate the ability to feed andincinerate the waste and to gain experience with the sanplingprotocols specified
• Two full waste test burns of nominally ID-hour duration with thewaste fired at about in and 18 kg/hr (2? and 3'? 1h /h r ) tospecif ical ly address the test objectives
Results of the tests are summarized in this paper.
FACILITY DESCRIPTION, WASTE CHARACTERIZATION. AND SYSTEM OPERATION
The rotary kiln incineration system at the CRF consists of a rotary kilnprimary combustion chamber, a fired afterburner, and a primary air pollutioncontrol system consisting of a venturl scrubber, wetted elbow, and packedtower scrubber. In addition, a backup air pollution control systen (APCD)consisting of a carbon-bed absorber and a HEPA filter is in place. Theprimary APCD might be considered reflective of what might exist in an actualcommercial or industrial Incinerator. The backup system is in place to
ensure organic pollutant and part iculate emissions to the atmosphere arenegligible. A schematic of the systen is given in Figure 1.
For these tes ts , wastff was introduced at the feed face through the frontface lance with a diaphragm-type punp, while aux i l ia ry fuel (propane) wasf i red through a burner located at the transfer duct end of the kiln. Theafterburner was a lso fired with aux i l ia ry fuel.
Table 1 summarizes the nominal incinerator operating conditions for eachof the tests performed. For all four, propane was f ired in the ki ln and theafterburner to maintain the k 1 1 n at about 1800°F and the afterburner at about2000°F. This corresponded to heat inputs of about 260 to 350 kW (0.9 to1.2 x 106 Btu/hr) in the kiln and about 470 to 560 kW (1.6 to 1.9 x106 Btu/hr) in the afterburner for all four tests.
The amount of waste fed into the kiln was monitored by recording thechanges in the waste container weight reading. The feedrates fluctuated overa wide range, with mean rates of 17 kg/hr (38 Ib/hr) on September 9; 10 kg/hr(22 Ib/hr) on September 20; and 18 kg/hr (39 Ib/hr) on September 21 , 1985. co
System residence times were calculated based on volumetric f lowratemeasurements using a helium tracer system ( 1 ) and the assumption that the '~'kiln and afterburner chamber temperatures were isothermal and equal to the 0single point measurement noted in Table 1. The calculated residence time in othe kiln main chamber was 5.7 sec for the blank burn, 5.3 sec for the Qminiburn, and 4.9 and 6.0 sec for the two stillhottoms waste full hums.Residence times in the afterburner were 2.1, 1,9, 1.8, and 2.3 sec for therespective tests.
The generic composition of the toluene stil lbottoms waste based onprevious data developed by the Vertac Chemical Company (?) and the physicalcharacter ist ics of the waste based on analysis performed on a sample nf thewaste at the CRF are given in Table 2. The waste was also analyzed for theorganic and trace element priority pollutants. Results of these analyses aregiven in Table 3. Specific analyses for the Principal Organic HazardousConstituent (POHC) in the waste, 2,3,7,8-TCDD, showed that it contained37 ppm of this compound.
Signif icant problems were experienced with attaining and maintainingwaste feed throughout the test program. Specific problems included continuedfeed lance clogging, due to carbon buildup (coking of the waste material), inthe lance, with pump check valve seal failure, and with the ability to pumpwaste. The feed lance clogging problem was solved by cofeeding water withthe waste so that when the lance clogged it would heat and vaporize thewater, thereby clearing the clog. Feed 1 1 n e clogging and check valve sealsticking were temporarily solved by cleaning a 1 1 feed line components withsolvent (toluene). However, in retrospect,the choice of a diaphragm pump forthis waste was inappropriate. The waste was waxy and very viscuous at roomtemperature. Only at about 95°C (200°F) would it flow sufficiently to beconsidered punpable. Hot water heating coils were ininersed in the waste forthese tests; however, pumping problems persisted. Perhaps a pump of another
Fiyu re 1. S i m p l i f i e d rotary k i l n system schematic.
0 0 0 1 7 9
TABLE 1. INCINERATOR SYSTEM OPERATING CONDITIONS
Kiln operation
Prootne he*t Input, kU(10b Btu/hr)
U«fte feedr*te, kg/hr(Ib/hr)
Mtste t<e«t Input, ku(10» Btu/hr)
Eult 9*1 teiiiper*ture, •CCF)
He—In*) r»lldenc» tine ^ec*
Afterburner opentlon
Proofne he*t Input, kw(Mr Btu/hr)
Exit 9*1 te-per«ture, •CcnNonlnJl residence time src*
APCD operation
System —ter —keup rite. L/mtn(9P>)
Syster bloxdown rite, L/«ln<W")
Scrubber liquor pH
Venturl pressure orop, kP<(in. HC)
Venturl eilt ustwprrtture, •CCF)
Picked tower pressurp drop, kPa(In. UC)
Picked tower cult n»twiper*lure, •CCM
nack'iroun't( t /4 /H
INSO ( 1 1 1
flange
?6n to ?<»o(O.S to 1 .0 )
<7i) to sno( 1 . 6 to 1 . ? )
\7 tn P(3.2 to « .<>
f>.H to 1 . 1( 1 . 8 to ?.«)
8.< to H.S
in.» to in.q(43 to 4<)
1 1 . 1 ' ) to n.'.u( l . < 1 " ?.ll)
humS' 1 4 1 ) )
Av<*riH|p
?nn(0.')«>)
nn
00
qSI)( 1 7 - , 1 1 )
•>.1
Oil)(l.M)
1 1 7 0(?n<n)
?.l
15«.n>
B.7( ? . ? >
1 1 . 5
in.?«]»
?v( i^»
0.41( l .H)
/H(I'.')
n'i
Ran
inn(n.n
( 1 H
37 to ini( 0 . 1 3 to 0.35)
<40( l .S
1(?.?
«.q( 1 . 3
B.O
8.7(33
D.in( 1 - 7
li| 1 hi> hr
MInthurn(••/•I/US
<5 to IS
np
tn wnto i.n)
R to 71to 60)
to sunto I . I )
n to nto «.•»)
to B.3to 2.7)
to B.7
to 10.0to <n)
to n.wto ?.())
"•o'o
,'H)
Avpr.nip
?.'n(0 .7? )
1 7(3B)
77(0.7f>)
qiO(IB?II)
5.3
470( 1 . 6 )
1 1 7 0(70")0)
1 . °
15(3.1)
1.7.1.1
8.?
9.S(3H)
HO( 1 7 6 )
0.40l.h
7H(in)
r..o.^-
ririt(<»
1030
Range
370 to( 1 . 1 tn
0 t(0 to
0 to 1 1 4(0 to 0.39)
wa to( 1 . 7 to
t.S t(?.S to
3.« t(0.9 to
B.O to
7."> to(30 to
0.47 to( 1 . ° to
m
full/?0/n«
to 71
440
1 .5 )
o 7556)
510Z.O)
0 30?.«)
o 1 33.4)
8.6
10.040)
1 . 35.7)
humi'30)
Atertg1'
3fl4( 1 . 3 )
10(??)
44(0.15)
<)fl0(1BOO)
4.4
560( 1 . 4 )
1 1 1 0(?030)
1.8
71(5.5)
H.7(Z.3)
8.?
R.6(35)
RI( 1 7 W )
1 .0( 4 . 1 )
HO( 1 7 M
Seconn full >•( •» /71/H'>
1 7 3 S to ? 1 1
R<nqe
?<»n to 350( 1 . 0 to 1 . 7 )
7.7 to 40(6 to B7)
1 7 to 1RO(0.04 to 0.6(1)
500 to 560( 1 . 7 to 1 . 4 )
6.nl to 73(l.fl to 6.0)
4.5 to 1 1( 1 . 7 to 7.B)
6.fl to B.R
7.0 to 4.7(7H to 34)
0.35 to 1 . 30.4 to 5.4)
iurn
1 0 1
Avpriiqp
310( 1 . 1 )
1 H(30 )
HO(0.77)
440(inni)
6.0
570( 1 . 1 )
1 1 1 0(?030)
?.3
16«.3)
a . 7( 7 . 3 )
B.?
B.5( 3 4 )
"7( 1 H O )
n.B5( 1 . 4 )
BI( 1" ! )
TABLE 2. STILLBCTTOMS W A S T E GENERICC O M P O S I T I O N ( 2 ) AND P H Y S I C A LC H A R A C T E R I S T I C S
CompoundConcentration
(percent)
Methanol
Toluene
Oichlorobenzenes
Tnchlorobenzenes
2,4,5-tri chloroani sole
Na-trichlorophenol
D-i chloronethoxybenzene
2,4,5-T, Na salt
1
8
1.5
1.5
56
7
16
7
ParameterValue
(percent)
B u l k dens i ty , g/m1 1.37
Lass on d r y i n g , percent 13.2
Ash 5.1
Heating value, MJ/kg 16 .11(Btu/lh) (6945)
TABLE 3. COMPOSITION OF THE STILLROTTOMS WASTE
Concentrations Detection limitConponent (ppn, wt) (ppit, wt)
Vo la t i le organic pr ior i ty po l lu tan ts
Methylene chloride1,1-dichloroethylene1,1-dichloroethanet-1,2-dichloroetrtyleneChloroform1,2-dichloroethane1,1,1-tr lchloroethaneCarbon tetrachlorideBromochloromethane1,2-dich'Ioropropylcnet-1,3-dichloropropyleneTrichloroethyleneBen2ene1,1,2-trlchloroethaneBronofonnTetrachloroethylene + tetrachtoroethaneChlorobenzeneToluene
Semvo'lati 'e organic priori ty pollutants
1,2-dich'lorobenzene1,2,4-trlchlorobenzeneAH other base/neutral s e m 1 » o 1 a t 1 1 e
prionty pollutants1,2-dichlorophenol4-0*11 oro-3-niethyl phenol2,4,6-tnchlorophenol2,4-dinitrophenol4-nitrophenol2-nietny1-4,6-dinitropheno1PentachlorophenolA l l other acid semivolatHe priority
pollutants
Trace Elenents
Antimony, SbArsenic, AsBeryl Hun, BeCarlmun, CilChroniluin, CrCopper, CuLead, PbMercury, HgNickel, N1Selenium, SeSilver, AgThallium. HZinc, An
277NONONONONONONONONONONONONONDNONO
159,000
2,6903,410
NO
159SOTOTONDNONONO
NONONONONONO4NONONONONONO
4242708442427042844242
1 1 042708442—
,.-
500
—500300300500500500100
213111111111
10
^0 denotes not detected at the detection limit noted.
design, such as a p rogress ive cavity pump, would have prov ided betterservi ce.
SAMPLING AND ANALYSIS PROTOCOLS
The combustion gas generated during each test was monitored at var inuslocat ions in the system for CO, CO;? 0^, N0^, total hydrocarbon (THC), H C 1 ,part iculate, and trace semi vo lat i le organic compounds, most importantly2,3,7,8-TCDD. In addit ion, grab samples were obtained of the waste feed, thescrubber system blowdown liquid, and the ash col lected in the ash pit duringthe tests. Ambient air sampling, both in the high-hay incinerator room andin the outside vicinity of the CRF was also performed. Figure 2 summarizesthe sampling locations and types of samples obtained.
Waste samples were analyzed for 2,3.7,8-TCDD by dilution, cleanup, andhigh resolution gas chromatography/low resolution nass spectrometry(HRGC/LRMS); for the halogenated volatile organic priority pollutants bydilution, purge and trap GC/election capture detector (ECD) in accordancewith Method 8010 ( 4 ) ; for the semivolatile organic priority pollutants hydilution, cleanup, and HRGC/LRMS in accordance with Method 8?70 (4) ; and for ^the priority pollutant trace elements by acid digestion and atomic absorpt ion 00techniques (4 ) . v-
0Kiln ash and hlowdown water samples were analyzed for polychlorinated —
dibenzo-p-dioxins (PCDDs) and polychlon'nated dihenzofurans (PCDFs) ofchlorine substitution 4 through 8, and for 2,3,7,8-TCDD, by benzeneextraction, extract concentration and cleanup, and HRGC/HRMS.
0
Blowdown water samples were also analyzed for the halogenated volat i leorganic priority pollutants by purge and trap GC/ECD in accordance withMethod 8010 (4 ) ; for the semivolat i le organic priority pollutants by benzeneextract ion, extract concentrat ion, and HRGC/LRMS in accordance withMethod 8270 (4); and for the priority pollutant trace elements hy atomicabsorption (4) .
Modified Method 5 (MM5) train samples were benzene extracted, extractsfor all train components combined, concentrated, and subjected to extractcleanup procedures (5 ) . These extracts were then analyzed for 2,3,7,8-TCDDby HRGC/LRMS. In addition, extracts for the four simultaneous MM5 trainsoperated downstrean of the scrubber system for the two full-burn tests werecombined and analyzed for 2,3,7,8-TCDD in accordance with Method 8280 (4).The samples from this area of the system, the "virtual stack" or "E-Duct",are very important since these data will be used to design future systems.
TEST RESULTS
Levels of O^, CO^, CO, and N0^ In the flue gas at the afterburner exitand in the stack for the four tests performed are summarized in Table 4. Asshown, all tests were performed at high excess air; flue qas 0^ was in the10 to 17 percent range in the afterburner exit and in the 13 to 17 percentrange in the stack. CO emissions were always low, <10 ppm, as were N0^
Ill
Parameter
CO^
02
CO
NO,
HC1
THC
Semvolatorganicsincludinc2,3.7,8-T
Waste
Kiln ash
Scrubberblowdown
(<clar^liln
I Z 1
i
3,4,8 Zirconium oxide Continuoussensor
3,4,8 NDIR Continuous
3,4,8 Chemilluminescence Continuous
6 Colorimetric Continuous
6,7 Plane ionizatdetector
ile 3,4,6,8 Modified Meth(MM5) (3)
rCDD
1 Grab
2 Grab 8 compositesafter entirehum series
5 Grab
1 3 1
Test?oints
3,4,8 NDIR
MterDurner
Ti « >
Methodolog
•entur licrutiOtr/•ettedelDCr
PdcieilloxtrscrubBcr
1
(5)
/
ion
od 5
Cordon
fi l ler
(61 in
Sampleduration
Continuou
Continuous3
10 hours(7 dscm)(?50 dscf
8 composiafter entburn sen'
H£PXnittr
S
2
2
) 42
tesirees
——1 ID f*n )————
1
No. ofsamples
--
at test pt 3at test pt 4at test pt 6at test pt 8
3
8
8
... y»»
Bl
t^
00
0
00
^he two test points were monitored by one instrument on a 5-mintime-sharing basis.
Figure 2. Summary of the general sampling protocol
l eve ls , <30 ppn. The m iss ing data noted in TaMe 4 i l l us t ra tes anotherproblem experienced during the tests, that of cont inuing cont inuous monitorfa i lure. Although the CRF has two complete nonitoring systems (0^, CO^, CO,and N0^), during these tests only one of each set of instruments was work ingand even some of these work ing instruments would per iod ica l ly fa i l ,
Table 4 a lso noted the HC1 emission rates for those tests for wh ichthese were measured. For the miniburn, the HC1 emission rate was 0.45 kg/hr ,as measured by the continuous HC1 monitor at the E-duct; for the September 20full burn, the HC1 emission rate was 0.25 kg/hr, as measured both by the HC1monitor and by the MM5 trains operated at the E-duct. Both of these are lessthan the CRF permit level of 0.5 kg/hr.
Table 5 summarizes the part iculate and 2,3,7,8-TCDO emission levelsmeasured at various locations in the incinerator system for each of thetests. As shown in the table, particulate levels at both the kiln andafterburner exit were quite low during the background hum with propane fuelalone, as expected. Flue gas particulate levels for the tests with waste
TABLE 4. EMISSION MONITOR AND HC1 EMISSION RATE DATA
Parameters
Backgroundburn
9/4/85Miniburn
9/9/85
Firstfull hum9/20/85
Secondfull burn9/21/85
Afterburner e x i t :
Oo (percent)CO^ (percent)CO ( p p m )NOx ( p p m )
E-duct:
HC1 ( k g / h r )ContinuousAnalyzerMM5 train
158
-.2
30
127
<1020
0.45
104
<1010
0.25
0.25
174
<1020
O? (percent)CO^ (percent)CO ( p p m )NOx (ppm)
177
<10
183
30
138
a—denotes monitor not operating or measurement not made.
TABLE 5. PARTICULATE AND 2,3,5,8-TCDD EMISSIONS AND 2,3,7,8-TCDD ORE
Sate and test
Bac<3'auod burn
Ki ln ex i t ;
Afterburnerexit :
E-duct:
Stack;
•4ini5urn 9/9/85
Kiln exi t :
tfteraurnerex i t :
FJH Sum 9/20/B5
Kiln exit:
A'terburnerexi t :
E-duct:
Stack :
Full aurn 9 / 2 1 / 3 5
Ki ln exit:
Afterburnerexi t :
E-duct:
Stack:
' o c a t ' o n
9 / 1 / 3 5
Tram 1Tra in 2
Train 1Train 2
Tap trainBotton trainLeft trainDignt train
East triinSouth train
T^am ITrain 2
T 'a in 1Train 2
Train 1Train 2Average
Train 1Tram 2
Too trainBottom trainLett t ra inSight trainAverage
East trainSouth tramAverage
Tram 1Train 2
Train 1Train 2Average
Top trainBottom trainLeft trainRight tr*1n
East trainSouth trainAverage
Particu
("g'dscnas "easjred)
0.280.50
0.833.4
.-b—b-.6—S
2.3o.4
463175
5852030
2.711 .462.39
371
266564291251343
38.456.047.2
7531940
154199176
<0.l52.3
10.8<0.13
72.6208140
lal:t emissions
'mg/ ' jscmcorrect?!)7 percent
1.97.9
8.11 .4
132378255
to,1,) a
2.3,7.8--':30emissions(ng/dsc" ' )
<3.95<0.36
<1.7<0.43
<0.18<0.24<0.31<0.31
<0.21<0.l0
<0.74< 1 . 4
<13< 1 1
<0.55<0.17
<3.8<1.3
<0.430.51<2.50.55
<2.3< 1 . 5
<6.4<2l
<3.9<2.8
<1.9<2.0<2.2<0.76
<1.5<1.6
2,3,7,8-TCDO 3
Rase4 onheliu" "icer
>99.99995>99.99991
>99.9984>99.99B6
>99.°W2>99.99998
>99.99903>99.99967
>99.99982>°9.99979>99.99896>99.99977
>99.99907>99.99945
>99.99964>99.99988
>99.99956>99.99969
>99.99969>99.99967>99.99864>99.99988
>99.99975>99.99973
RE (percent)
Pasedon f'1'JcgiS
ve loc i ty
>99.90987>9<l.99985>99.99926>99.99983
>99.99916>99.99951
>99.99974>99.99973>99.99970>99.999897
>99.99974>99.99973
'0; meter "ot functioning properly. Values, when given, •rt ettlnntM.^0 filter* tre used In the £-<luct trains for this test.tEvfdence of * signfficm sampling train teak •is discovered »fter sampling Mas complete. Oatawere considered invalid for partlculate measurenents.
10
feed were highly var iab le and ranged fron several to severa l hundred ng/dsc"^.Paniculate levels at the vir tual s tack (E-duct) were as high as 340 ^g/dsc"!for one test . Due to technical f ac to rs , and sines the 0^ monitor at th islocation was not operat ing properly at the time of the test , accurate f igurescorrected to 7 percent 0^ cannot be der ived from the raw data. Since resul tsare uncertain, further work on measurement of par t iculate emissions fromdioxin contaminated was te is needed.
Part iculate emissions at the system stack (after the High Ef f ic iencyPart iculate Fi l ter) were also indicated as being much higher thananticipated. The va lues are 5 to 15 times higher than design values and are,therefore, suspect. Further testing is needed to determine the nature andsource of the part iculate, if they are indeed as high as indicated.
Flue gas levels of 2,3,7,8-TCDD were less than method detection limitsat all locations for all tests. These levels correspond to the ORE valuesnoted in Table 5 for the tests with waste feed. Two sets of ORE values arenoted in the table for the E-duct and stack locations. These correspond to i .two different measures of flue gas flowrate. One of these was based on aheliun tracer injection system; the other was based on the MM5 train veloci tymeasurements. The data in Table 5 suggest that 2,3,7,8-TCDO DRE wasgenerally greater than 99.9997 percent in the virtual stack, which would 0likely correspond to the stack of an actual hazardous waste incinerator. 0
CO
0Method detection limits were not low enough to establish that greater
than 99.9999 percent ORE was achieved either at the virtual stack or at thesystem stack. Therefore, the extracts from the four MM5 trains operated atthe virtual stack for the two full-burn tests were combined and reanalyzed inan attempt to achieve better detection limits. Calculated 2,3,7,8-TCDDlevels for the virtual s tack, and corresponding 2,3,7,8-TCDD DREs, based onthe combined extract analyses for the second full burn ( 9 / 2 1 / 8 6 ) , are givenin Table 6. The data for the second full burn clearly show that greater than99.9999 percent DRE was achieved. The extracts for the first full burn werespiked with an order-of-magnitude higher level of recovery standard thanappropriate by the of fs i te laboratory which originally analyzed theindividual train extracts. As a consequence, method detection limitscorresponding to ng/dscm of flue gas were not better than for the individualtrain analysis data, as summarized in Table 5.
The kiln ash and the scrubber blowdown water from this entire testseries was analyzed for PCDDs and PCDF of chlorine substitution 4 through 8.The kiln ash samples were generally devoid of PCDDs and PCDF to detectionlimits ranging from 3 to 40 ppt, as shown in Table 7. Similarly, the data inTable 8 show that scrubber blowdown samples were devoid of all PCDDs andPCDFs; except octa-CDDs which were present at 0.07 ppt. This is notsurprising since octa-CDDs are relatively common in environmental samples.
Results from these analyses are summarized in Table 9 in the torn of2,3,7,8-TCDD equivalents. The 2,3,7,8-TCDD equivalent of a given CDD or CDFhomolog is defined as the product of its concentration with a toxicequivalent factor (6). Toxic equivalent factors have been defined by EPA's
11
TA3LE 6 . 2,3,7,8-TCDD EMISSIONS AND DRE BASED ON COMBINED E-DUCTTRAIN EXTRACTS
2.3 ,7 ,8-TCDD DRE
2,3,7,8-TCDDemissions Based on Based on
Test date (ng/dscm) helium tracer f lue gas velocity
Full burn 9/21/86 <0.39 >99.999989 >99.999991
TABLE 7. LEVELS OF PCDD AND PCDF IN KILN ASH SAMPLES
Concentration8 (ppt)13
Analyte Sample 1 Sample 2 Sample 3 Sample 4
2.3.7,8-TCDO ( 1 3 ) (10) ( 5 . 6 ) ( 2 8 )TCDOs ( 1 3 ) (10) ( 5 . 6 ) ( 2 8 )Penta-CUDs (28) ( 6 . 5 ) ( 4 . 2 ) ( 1 6 )Hexa-CCDs ( 7 . 4 ) ( 4 . 5 ) ( 5 . 0 ) ( 3 7 )Hepta-CDDs ( 1 4 ) ( 6 . 3 ) ( 3 . 4 ) ( 3 . 4 )Octa-CDDs (44) (18) ( 1 5 ) 235
2.3,7,8-TCDF ( 7 . 0 ) ( 1 6 ) ( 7 . 1 ) ( 1 0 )TCDFs ( 7 . 0 ) ( 1 6 ) ( 7 . 1 ) ( 1 0 )Penta-CDFs ( 1 1 ) ( 2 . 7 ) ( 1 . 7 ) ( 6 . 4 )Hexa-CDFs ( 4 . 6 ) ( 2 . 8 ) ( 3 . 1 ) ( 7 . 4 )Hepta-CDFs ( 1 2 ) ( 6 . 2 ) ( 3 . 4 ) ( 8 . 4 )Octa-CDFs (3 3 ) ( 2 1 ) ( 1 5 ) (40)
lumbers in parentheses denote analyte not detected to thedetection limit noted in parentheses.
b! ppt = 1 pg/g.
12
TABLE 8. LEVELS OF PCDD AND PCDF IN SCRUBBER BLOWOOWN SAMPLES
Concentration3 (ppt )^
Analyte
2,3,7,8-TCDDTCDDsPenta-CCDsHexa-CCDsHepta-CDDsOcta-CDDs
2.3,7.8-TCDFTCUFsPenta-CDFsHexa-CDFsHepta-CDFsOcta-CDFs
Sample 1
(0.005)(0.06)(0.04)(0.03)(0.02)0.07
(0.02)(0.1)(0.02)(0.02)(0 .1 )(0 .1 )
Sample 2
(0.02)(0.08)(0.05)(0.04)(0.04)0.04
(0.01)(0.07)(0.02)(0.06)(0.02)(0.08)
Sample 3
(0.02)(0.09)(0.04)(0.04)(0.03)0.07
(0.02)(0.1)(0.07)(0.06)(0.03)(0.06)
Sample 4
(0.04)(0.09)(0.02)(0.03)(0.05)0.07
(0.02)(0.06)(0.03)(0.06)(0.03)(0.04)
lumbers in parentheses denote analyte not detected to thedetection limit noted in prentheses.
b! ppt = 1 pg/ml.
TABLE 9. 2,3,7,8-TCDD EQUIVALENTS IN THE SCRUBBERSLOWDOWN WATER
cHonolog
Tetra-COOPenta-CDOHexa-CDDTetra-CDFPenta-CDFHexa-CDF
Total
Maximunb1owdown
oncentration(PPt)
(0.09)(0.05)(0.04)(0.02)(0.07)(0.06)
Toxica equivalent
factor(6)
10.50.040.10.10.01
2,3,7,8-TCDDequivalents
(PPt)
(0.09)(0.025)(0.0016)(0.002)(0.007)(0.0006)
(0.13)
lumbers 1n parentheses indicate less than thecor responding detection l i m i t ; 1 ppt equals 1 pg/ml
13
Chlorinated Dioxin Workgroup for several CDDs and CDFs and are based onstructure activity relationships which are used to estimate relat ivecarcinogenic, reproductive, and biochemical effects among 2,3,7,8-TCDD andother CDDs and CDFs. The 2,3,7,8-TCDD equivalent of a mixture is the sum ofthe 2,3,7,8-TCDD equivalents associated with each homolog in the mixture.
The 2,3,7,8-TCDD equivalents noted in Table 9 for the scrubber blowdowncorrespond to the maximum concentration of any homolog detected in any of thesamples analyzed. For conservatism, those homologs not detected were assumedto be present at the maximum detection limit experienced. Table 9 shows thatthe scrubber blowdown contained at maximum 0.13 ppt of 2,3,7,8 TCDDequivalents.
The scrubber blowdown was also analyzed for the organic and traceelement priority pollutants. Results are summarized in Table 10. As shown,no organic priority pollutant was present in the blowdown at levels greaterthan 10 ppb. In addition, none of the trace elements was present atconcentrations which would cause the blowdown water to be considered EP(Extraction Procedure) toxic. Based on a 1 1 analytical data, the blowdown owould not be considered a hazardous waste. ^
CONCLUSIONS v"0
A series of incineration experiments was performed with the Vertac 0Chemical Company's toluene still bottoms waste from trichlorophenol oproduction. This waste is one of the more well known of thedioxin-contaminated wastes presently in existence. Samples of the wastetested in this study contained an average of 37 ppm 2,3,7,8-TCDD (37 ug/g).
Three incineration tests were performed during September 1985. All wereperformed in the CRF rotary kiln incineration system with a nominal wastefeedrate of 20 kg/hr.
With regard to the principal objectives of these tests, the followingcan be concluded:
o 2,3,7,8-TCDD DRE, based on the combined extracts from the four MM5trains at the virtual stack, was greater than 99.9999 percent forone test. For the other test, method detection limits preventedquantitating that better than 99.9998 percent ORE was achieved.
e Accurate determination of particulate emissions at the virtual stackand system stack was not achieved. Further research is needed toobtain data on the amount, nature, and source of particulateemissions from these sources.
• HC1 emissions In the virtual stack ranged fron 0.2 to 0.45 kg/hr.These results are less than the RCRA standard of 0.5 kg/hr.
• Scrubber blowdown has characteristics which allow it to be delistedas a hazardous waste.
14
TABLE 10. PRIORITY POLLUTANT COMPOSITION OF THE SCRUBBER RLOWnO^N MA^ER
ConponentConce" t ra t1on
(PP'), w t )a
Detectionl i n n t
(Ppb . wt}
V o l a t i l e o r g a n i c p r i o r i t y p o l l u t a i t s
Methylene chlor ide NO 12.61 .1 -d ich 'o roe tny lene "0 2.61 . 1 - d i c h l o c o e t h a n e ^.\ 2.6t - l ,2-dich' loroetny1ene NO 2.6Chloroform NO 4.21.2-dichloroethane 'ID 5.01,1,1- tnchloroethane ND 2.6Carbon tetrachloride NO 2.6Bromodichloronethane TO 4.21,2-dichloropropylene ND 2.6t- l ,3-dic»i1oropropy1ene NO 5.0Trich1oroethy1ene NO 2.6Benzene NO 2.61.1,2-tr lchloroethane NO 6.8Bromo^orrn NO 4.2Tetrachloroethylene + tetrachloroetnane W 5.0Chlorobenzene NO 12.6
Se'-nvolati I e o r g a n i c p n o r i t y pon'J tants
All sase/neutral seniivolatlle pnoritypo1 lu tants
A-chloro-S-nethyl phenol2.4,6-trichlorophenol2,4-dinitropnenol4-mtrophenol2--nethy1-4,6-dinitropheno1PentachloropienolAl l other acid sei"1 volat i le priority
pol iJtants
NO
NONONONONONONO
5
50303050505010
EP tocic i tyconcentrat 'on
(ppn, wt) (ppn, wt) Umit (ppn)
Trace ele-nents
Ant imony, AbA r s e n i c , AsB e r y l l i u m , 3eC a d m i u n , CdChrwium, CrCopper, CuLead, PbMercury, HgN i c k e l , N1Selenium, S<Si lve r , AgT h a l l i u m , T1Z i n c , Zn
NONONONONO4°lbNO!&NOND
NOND
21311111111
110
5—15»»
50.2.15..••
^0 denotes not detected; duplicate samples analyzed.hFound •in only one sample; not detected In the others,
15
The above conclusions suggest that incineration should be considered av iab le disposal method for this sti l lbottons waste, given that appropriatesafeguards are employed. The data in this study conf irm that an incinerator,operat ing under proper condit ions, can achieve greater than 99.9999 percentDRE for 2,3,7,8-TCDD, wi th HC1 emissions helow the regulatory limit.
ACKNOWLEDGEMENTS
The work reported in this paper was supported by E P A ' s Hazardous WasteEnvironmental Research Laboratory under EPA Contracts 68-03-3128 and68-03-3267. The guidance and support of the former EPA Project Off icer,Richard A. Carnes, is gratefully acknowledged.
REFERENCES
1. Carnes, R. A. and F. C. Whitmore, "Characterization of the Rotary KilnIncineration System at the USEPA Combustion Research Facility (CRF) , " ^Hazardous Waste, Vol. 1 , No. 2. 1984, p 225.
2. Federal Register, Vol. 51 . No. 106. June 3, 1986, pp 19850-19863. ^~0
3. "ASME MM5 Sampling Methodology for Chlorinated Organics," Draft Mo. 4, 0American Society of Mechanical Engineers, New York, October 1984. Q)
4. "Test Methods for Evaluating Solid Waste: Physical/Chemical Methods,"EPA SW-846, 2nd ed., July 1982.
5. "Analytical Procedures to Assay Stack Effluent Samples and ResidualCombustion Products for Polychlorinated Dibenzo-p-dioxins (PCDDs) andPolychlorinatedl Dibenzofurans (PCDFs) , " ASME Environmental StandardsWorkshop, September 18, 1984.
6. EPA Chlorinated Dioxins Workgroup Document, "Interim Procedures forEstimating Risk Associated with Exposures to Mixtures of ChlorinatedDioxins and Dibenzofurans (CDDs and CDFs) , November 1985.
16
PILOT-SCALE INCINERATION OF A DIOXIN-CONTAINING MATERIAL
Larry R. Water- land, Robert W. Ross, II,Thomas H. Backhouse, Ralph H. Vocque,
and Johannes W. LeeAcurex Corporation
Combustion Research FacilityJefferson, Arkansas 72079
Robert E. MournighanU.S. Environmental Protection Agency
Hazardous Waste Engineering Research LaboratoryCincinnati, Ohio 45268
^0\\—
0
ABSTRACT
A series of three tests directed at evaluating the incinerabiUty of the °toluene stiUbottoms waste from trichlorophenol production previously gener- ^ated by the Vertac Chemical Company were performed in the Combustion ResearchFacility (CRF) rotary kiln incineration system. This waste contained 37 ppm2,3,7.8-TCDD as its principal organic hazardous constituent (POHC). Flue gas2,3,7,8-TCDD levels were less than detectable at all locations sampled.Corresponding incinerator destruction and removal efficiencies (DREs) weregreater than 99.9997 percent, based on individual sampling train analyses. Byanalyzing combined extracts from four simultaneous sampling trains, it wasconcluded that 2,3,7,8-TCDD DRE was indeed greater than 99.9999 percent.These results suggest that land-based incineration of the Vertac waste iscapable of achieving the required DRE and should be considered a treatmentoption for this waste.
INTRODUCTION
One of the primary functions ofthe Environmental Protection Agency's(EPA) Combustion Research Facility(CRF) is to perform incineration test-ing of troublesome hazardous wastes tosupport decisions regarding whetherIncineration Is a proper waste treat-ment and disposal option. One classof such wastes 1 s those contaminatedwith 2,3.7,8-tetra-chlorodibenzo-p-dioxin (2.3.7.8-TCDD or dioxin).
One well-established, highlydioxin-contaminated waste is the tol-uene still bottoms from trichloro-phenol production previously gener-ated and currently being stored, un-til a decision regarding appropriatetreatment and disposal Is reached, atthe Vertac Chemical Company inJacksonville, Arkansas. The gener-ator is currently considering onsiteincineration in a mobile incineratorsystem as an avenue for disposal ofthis waste and wishes to have a
permit for a trial burn issued. Theprimary object ive of the tests re-ported herein is to evaluate the1nc ine rab i1 i t y of the Vertac toluenesti l lbottoms waste by determiningwhether 99.9999 percent ORE could beachieved, as required by current reg-ulations. Results of these incinera-tion tests could, in turn, be used tosupport any subsequent permit decisi-on.
All tests were performed in theCRF rotary kiln incineration system.The rotary kiln incineration systemat the CRF consists of a rotary kilnprimary combustion chamber, a firedafterburner, and a primary air pol-lution control system consisting of aventuri scrubber, wetted elbow, andpacked tower scrubber. In addition,a backup air pollution control system(APCS) consisting of a carbon-bedabsorber and a HEPAplace. The primaryconsidered reflectiveexist in an actualindustrial incinerator. The backupsystem is in place to ensure organicpollutant and particutate emissionsto the atmosphere are negligible.Results of the tests are summarizedin this paper.
PURPOSE
As noted above, the purpose ofthe tests was to specif ically de-termine whether the still bottomswaste could be incinerated in a well-operated rotary kiln Incinerator,giving 99.9999 percent dioxin ORE,with no contaminated residualstreams.
The test programsisted of a totalburns. These trialof the following:
filter is inAPCS might beof what mightcommercial or
performed con-of four trialburns consisted
A blank burn wi th the incin-erator f ired with aux i l ia ryfuel (propane) only to es-tablish background emiss ionlevels of pollutants of con-cern
A miniburn of short duration(4 hours) with waste f i redat nominally 17 kg/hr (38Ib/hr) to demonstrate theability to feed and inciner-ate the waste and to gainexperience with the samplingprotocols specified
Two full waste test burns ofnominally 10-hour durationwith the waste fired atabout 10 and 18 kg/hr (22and 39 Ib/hr) to specif ical-ly address the test objec-tives
APPROACH
For these tests, waste was in-troduced at the feed face through thefront face lance with a diaphragm-type pump, while auxiliary fuel (pro-pane) was fired through a burnerlocated at the transfer duct end ofthe kiln. The afterburner was a lsofired with auxiliary fuel.
For all four tests, propane wasfired in the kiln and the afterburnerto maintain the kiln at about 180U°Fand the afterburner at about 2000°F.For the tests with waste feed, feed-rates fluctuated over a wide range,with mean rates of 17 kg/hr (38Ib/hr) for the miniburn; 10 kg/hr(22 Ib/hr) for the first full burn;and 18 kg/hr (39 Ib/hr) for the sec-ond full burn.
System residence times were cal-culated based on volumetric f lowrate
measurements using a helium tracersystem (2) and the assumption thatthe kiln and afterburner chamber tem-peratures were isothermal. The cal-culated residence time in the kilnmain chamber was 5.7 sec for theblank burn, 5.3 sec for the miniburn,and 4.9 and 6.0 sec for the twostillbottoms waste full burns. Resi-dence times In the afterburner were2.1, 1.9. 1.8. and 2.3 sec for therespective tests.
The generic composition of thetoluene stillbottoms waste based onprevious data developed by the VertacChemical Company (3) and the physicalcharacteristics of the waste based onanalysis performed on a sample of thewaste at the CRF are given inTable 1. The waste was also analyzed
for the organic and trace elementpriority pollutants. Results ofthese analyses are given in Table 2.Specif ic analyses for the PrincipalOrganic Hazardous Constituent (POHC)in the waste, 2,3,7,8-TCDD. showedthat it contained 37 ppm of thiscompound.
The combustion gas generatedduring each test was monitored atvarious locations in the system forCO, COg 02, NOx, total hydrocarbon(THC). HC1. paniculate, and tracesemi volatile organic compounds, mostimportantly 2,3,7,8-TCDD. In addi-tion, grab samples were obtained ofthe waste feed, the scrubber systemblowdown liquid, and the ash collect-ed in the ash pit during the tests.Ambient air sampling, both in thehigh-bay incinerator room and in theoutside vicinity of the CRF was also
Table 1. Still bottoms waste genericcomposition (3) and physi-cal characteristics. Table 2. Composition of the
still bottoms waste.
CompoundConcentration
(percent)Conctntr-ttion*
(PP", «rt)
Methanol 1Toluene 8Dichlorobenzenes 1.5Trichlorobenzenes 1.52,4,5-trichloroanisole 56Na-trichlorophenol 7Dichloromethoxybenzene 162.4,5-T, Na salt 7
ParameterValue
(percent)
Volltl le organic priority pollut«nti
Metnylene chloride 211Toluene 1S9.000All other olttllt org»n1c priority NO*
pollufnti
Senivolatile orginic priority pollutints
l.Z-dlchlorobtniene 2.6901.2.4-lrtchlorobefnene 3,<10All other o*se/neutr«1 sot volatile NO13
priority pollutintsAll other (dd t»l volltl 1( priority HD'-
pollutints
Tr»c« Eleaentt
Lfd, P6 4All other Apewidix V I I I met (Icentt NO"1
Bulk density, g/ml 1.37Loss on drying, percent 13.2Ash 5.1Heating value. MJ/kg 16.11
(Btu/lb) (6945)
•KB denotts wt defcttd it detection Halts frigingfroB 40 to 110 PDB.
^W BCTBtM not detected it » detection Unit of 500.PC.'NO denotes not detected •t detection Hilts rangingfro* 100 to 500 ppr.
^m denotes not detected it detection Hilts ringingfro- 1 to 10 ppB.
performed. Figure 1 summarizes thesampling locations and types of sam-ples obtained.
Waste samples were analyzed for2,3,7,8-TCDD by dilution, cleanup,and high resolution gas chromato-graphy/low resolution mass spectro-metry (HRGC/LRMS); for the halogen-ated volatile organic priority pollu-tants by dilution, purge and trapGC/electron capture detector (ECD) inaccordance with Method 8010 (4 ) ; forthe semi volati le organic prioritypollutants by dilution, cleanup, andHRGC/LRMS in accordance with Method8270 (4); and for the priority pollu-tant trace elements by acid digestionand atomic absorption techniques(4).
Kiln ash and blowdown water sam-ples were analyzed for polychlorinat-ed dibenzo-p-dioxins (PCDDs) andpolychlorinated dibenzofurans (PCDFs)of chlorine substitution 4 through 8,
and for 2,3,7,8-TCDD, by benzene ex-traction, extract concentration andcleanup, and HRGC/LRMS.
Slowdown water samples were a lsoanalyzed for the halogenated volat i leorganic priority pollutants by purgeand trap GC/ECD in accordance withMethod 8010 ( 4 ) ; for the semi volati leorganic priority pollutants by ben-zene extraction, extract concentra-tion, and HRGC/LRMS in accordancewith Method 8270 (4); and for thepriority pollutant trace elements byatomic absorption (4).
Modified Method 5 (MM5) trainsamples were benzene extracted, ex-tracts for all train components com-bined. concentrated, and subjected toextract cleanup procedures ( 1 ) .These extracts were then analyzed for2,3,7,8-TCDD by HRGC/LRMS. In addi-tion, extracts for the four simulta-neous MM5 trains operated downstreamof the scrubber system for the two
l-lyl
•rtue
HUM
»^wLew
»<!(»»
, urn»m»-
if) 1 1 1
Samplingpoint
12345678
Description
Waste feedKiln ashKiln exit flue gasAfterburner exit flue gasScrubber blowdownScrubber discharge flue gasCarbon bed exit flue gasStack flue gas
Grabsample
XX
X
CO, C02GZ, NOx
X
X
HC1
X
THC
XX
MM5 forTCDD
XX
X
X
Figure 1. Summary of the general sampling protocol.
full-burn tests were combined andanalyzed for 2,3,7,8-TCDD in accor-dance with Method 8280 (4) . The sam-ples from this area of the system,the "virtual stack" are very impor-tant since these data wil l be used todesign future systems.
PROBLEMS ENCOUNTERED
Significant problems were expe-rienced with attaining and maintain-ing waste feed throughout the testprogram. Specific problems includedcontinued feed lance clogging, due tocarbon buildup (coking of the wastematerial) , in the lance, with pumpcheck va lve seal failure, and withthe ability to pump waste. The feedlance clogging problem was solved bycofeeding water with the waste sothat when the lance dogged it wouldheat and vaporize the water, therebyclearing the clog. Feed line clog-ging and check valve seal stickingwere temporarily solved by cleaningall feed line components with solvent(toluene). However, in retrospect,the choice of a diaphragm pump forthis waste was inappropriate. Thewaste was waxy and very viscous atroom temperature. Only at about 95°C(200°F) would it flow sufficiently tobe considered pumpable. Hot waterheating coils were immersed in thewaste for these tests; however,pumping problems persisted. Perhapsa pump of another design, such as aprogressive cavity pump, would haveprovided better service.
RESULTS
Levels of QZ. COg. C0» and NOxIn the flue gas at the afterburnerexit and 1 n the stack for the fourtests performed are summarized InTable 3. As shown, all tests wereperformed at high excess air; fluegas Og was in the 10 to 17 percent
range in the afterburner exit and inthe 13 to 17 percent range in thestack. CO emissions were always low,<10 ppni, as were NOx levels, <30 ppm.Table 3 also notes the HC1 emissionrates for those tests for which thesewere measured. For the miniburn, theHC1 emission rate was 0.45 kg/hr, asmeasured by the continuous HC1 moni-tor in the scrubber discharge; forthe first full burn, the HC1 emissionrate was 0.25 kg/hr, as measured bothby the HC1 monitor and by the MM5trains operated at the scrubber dis-charge. Both of these are less thanthe CRF permit level of 0.5 kg/hr.
Paniculate levels at both thekiln and afterburner exit were quitelow during the background burn withpropane fuel alone, as expected.Flue gas particulate levels for thetests with waste feed were highlyvariable and ranged from several toseveral hundred mg/dscm. Paniculatelevels in the scrubber discharge wereas high as 340 mg/dscm for one test.Due to technical factors, and since
Table 3. Emission monitor and HC1emission rate data.
First SecondBickground full full
Bum Ninlburn burn burnPTincters »/«/8S 9/9/8S »/20/85 9/21/85
Afterburner tx1 t ;
Oy (percent)CO? (percent)CO (ppm)NO, (ppo)
E-duct:
HO (kg/hr)ContinuousAmiyierW6 li-tin
Stict:
fo (pTCMt)CO? (percent)CO (pp")NO, (ppi)
15a
—*30
..
—
177
<10"
127
<l020
0.«5
"
183
.-30
104
<1010
0.25
0.25
••
8..••
174
<1020
..
"
138-.
••
•••denotes •onitor not opertting or •easurenent not Mac.
the 02 monitor at this location wasnot operating properly at the time ofthe test, accurate figures correctedto 7 percent 0 cannot be derivedfrom the raw data. Since results areuncertain, further work on measure-ment of particulate emissions fromdioxin contaminated waste is needed.
Particulate emissions at thesystem stack (after the HEPA filter)were also indicated as being muchhigher than anticipated. The valuesare 5 to 15 times higher than designvalues and are, therefore, suspect.Further testing is needed to deter-mine the nature and source of theparticulate, if they are indeed ashigh as indicated.
Table 4 summarizes the 2 , 3 , 7 , 8 -TCDD emission levels measured at var-ious locations in the incineratorsystem for each of the tests. Asshown in the table, flue gas levelsof 2,3,7,8-TCDO were less than methoddetection limits at all locations forall tests. These levels correspondto the ORE values noted in Table 4.Two sets of ORE values are noted inthe table for the scrubber dischargeand stack locations. These corre-spond to two different measures offlue gas flowrate. One of these wasbased on a helium tracer injectionsystem; the other was based on theMM5 train velocity measurements. Thedata in Table 4 suggest that 2 , 3 , 7 , 8 -TCDD ORE was generally greater than9 9 . 9 9 9 7 percent in the scrubber dis-charge, which would likely correspondto the stack of an actual hazardouswaste incinerator.
Method detection limits were notlow enough to establish that greaterthan 9 9 . 9 9 9 9 percent ORE was achievedeither in the scrubber discharge orat the system stack. Therefore, theextracts from the four MM5 trainsoperated at the scrubber discharge
for the two full-burn tests werecombined and reanalyzed in an attemptto achieve better detection limits.Calculated 2,3,7,8-TCDD levels andcorresponding 2,3,7,8-TCDD DREs,based on the combined extract analy-ses for the second full burn aregiven in Table 5. The data for thesecond full burn clearly show thatgreater than 99.9999 percent DRE wasachieved. The extracts for the firstfull burn were spiked with an order-of-magnitude higher level of recoverystandard than appropriate by the off-site laboratory which originallyanalyzed the individual train ex-tracts. As a consequence, methoddetection limits corresponding to cong/dscm of flue gas were not betterthan for the individual train analy-sis data, as summarized in Table 4.
0The kiln ash and the scrubber 0
blowdown water from this entire test oseries was analyzed for PCDDs andPCDF of chlorine substitution 4through 8. The kiln ash samples weregenerally devoid of PCDDs and PCDF todetection limits ranging from 3 to40 ppt. Similarly, the scrubberblowdown samples were devoid of allPCDDs and PCDFs; except octa-CDDswhich were present at 0.07 ppt. Thisis not surprising since octa-CDDs arerelatively common in environmentalsamples, and the level measured wasquite low.
The scrubber blowdown was alsoanalyzed for the organic and traceelement priority pollutants. No or-ganic priority pollutant was present1n the blowdown at levels greaterthan 10 ppb. In addition, none ofthe trace elements was present atconcentrations which would cause theblowdown water to be considered EP(Extraction Procedure) toxic. Basedon all analytical data, the blowdownwould not be considered a hazardouswaste.
Table 4. 2,3,7,8-TCDD emissions and ORE
Oat? inii tut
Minlnurn
(lln (ift:
Afterburner»iH:
Ffrs t Fun Burn
Kiln »iU:
AfterburnerHit:
Scrubber i^ttemdischarge:
Stick:
Seconn Full Hum
(tin eitt:
AfterburnerdU:
Scruhhfr systemdischarge:
Stick:
Table 5. 2,3,7,8-TCDD emissions and DRE hasen on combined scruhherdischarge train extracts
Test d«t*
7,3fi
locttlon (n
Tr«ln 1Tr*fn ?
T r» fn 1Train ?
Tr»)n 1Tr»fn ;A«er*g«
Tr»tn 1T r» fn ?
Top trifnBottix" trtinL»H trtinBight tn1n*v»r*g»
East tntnSouth trtin»»er»9t
Train 1Tr»<n ;
Tr«1n 1Tr i fn 2*»»r<g»
Tnp TritflBotto" trtinLtft t r«1nBight trifn
E«$t tr»lBSouth trtinAverage
2,3.7,9-TCUO miss(ng/dic»)
,7,R-T iI ss ton 'g/'lic"'
<0.7«<1 .«
<l3< 1 1
<O.S5<0.17
<3.D< 1 . 3
<n.<3<0.51<2.5<0.5S
<?.3<1.5
<6.<<?1
<3.9<?.»
<1.0<;.o<?.?<0.76
< 1 . 5<1.6
Ions
?.3,7,8-TCDO t
CODi *iS"1 0") h»l\uw tracer
>'>9,'»9995>99,99991
>99.<984>99.99B6
>99.991^1^^>99.'»9998
>99.99903>99,99967
>9S.9998Z>99.99979>9fl.99896>99.99977
>99.99907>99.991«S
>99.<N96«>99.99988
>i)9.99956>99.99969
>99.99969>99.99967>99.99864>99.999H8
>99.9997S>99.99973
t.3,7.8-Ta>0
t«s*d on tanIfltuB tricT gal
W (perc'nt)
Ras"<rin flu* g-'<olocltj'
>99.99987>99.999fl5>99.999?5>99.999ft3
>99.99916>'»9.999S1
>99.9997<>99.99973>99.99970>99.99<)897
>99.99974>99.99973
ME
id on flu*••loctty
Full burn 9/11/86 <0.066
In summary, a series of Inciner-ation experiments was performed withthe Vertac Chemical Company's toluenestillbottoms waste from trichloro-phenol production. This waste is oneof the more well known of the dioxin-contaminated wastes presently in ex-istence. Samples of the waste testedin this study contained an average of37 ppm 2,3,7,8-TCDD (37 pg/g). Threeincineration tests were performed inthe CRF rotary kiln incineration sys-tem with a nominal waste feedrate of20 kg/hr.
with regard to the principalobjectives of these tests, the fol-lowing can be concluded:
• 2,3,7,8-TCDD ORE, based onthe combined extracts fromthe four MM5 trains in thescrubber discharge, wasgreater than 99.9999 percentfor one test. For the othertest, method detection lim-its prevented quantitatingthat better than 99.9998percent DRE was achieved.
• Accurate determination ofparticulate emissions at thevirtual stack and systemstack was not achieved.Further research is neededto obtain data on theamount, nature, and sourceof particulate emissionsfrom these sources.
• HC1 emissions 1 n the virtualstack ranged from 0.2 to0.45 kg/hr. These resultsare less than both the RCRAstandard of 1.8 kg/hr. andthe CRF penult limit of 0.5kg/hr.
The conclusions suggest tnat in-cineration should be considered aviable treatment method for thisstil lbottoms waste, given that appro-priate safeguards are employed. Thedata in this study conf i rm tnat anincinerator, operating under properconditions, can achieve greater than99.9999 percent ORE for 2 ,3 ,7 .8 -TCDO,with HC1 emissions below the regula-tory limit.
ACKNOWLEDGEMENTS
The work reported in this paperwas supported by EPA's HazardousWaste Environmental Research Labora-tory under EPA Contracts 68-03-3128and 68-03-3267. The guidance andsupport of the former EPA ProjectOfficer, Richard A. Carnes, is grate-fully acknowledged.
REFERENCES
1. American Society of MechanicalEngineers, 1984, AnalyticalProcedures to Assay Stack Eff lu-ent Samples and Residual Combus-tion Products for PolychlorinatedDibenzo-p-dioxins (PCDDs) andPolychlorinated Dibenzofurans(PCDFs), ASME Environmental Stan-dards Workshop, September 18.
2. Carnes, R. A. and F. C. Whitmore,1984, Characterization of the Ro-tary Kiln Incineration System atthe USEPA Combustion ResearchFacility (CRF), Hazardous Was te .Vol. 1, No. 2. p "22^
3. Federal Register, Vol. 51, No.106, June 3, 1986, pp 19850-19863.
Scrubber btowdownacteristlcs whichto be delisted asous waste.
4. Test Methods for Evaluating Solidhas char- Waste: Physical/Chemical Meth-allow it ods, EPA SW-846, 2hd ed., July
a hazard- 1982.