characterization of pic emission from comb of pentanchlorophenol

8/6/2019 Characterization of PIC Emission From Comb of Pentanchlorophenol

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Characterization of PIC Emissions om Combustion of Pentachloropheno-Treated Wood Wastes

PEER-REVEW

Suh Y. Lee, Joseph C. Vaenti, and Dennis G Tabor Acurex Environmental Corporation

4915 Prospectus DriveDurha, NC 27713

Robert V. Hendriks and C. W. LeeAir Poution Prevention d Contro Division

Nationa Risk Mnagement Research Laboratoryus Environmental Protection Agency

86 TW Aexander DriveResearch Triange Pk, NC 27711

89



INTRODUCTION

The use of wase wood as e for producing energy is a promising suppemen o fossi es for manyregions of he counry In addiion o recovering energy and conserving and space bing wasewood es aso miigaes goba warming creaed by fossi e combusion However he

environmena consequences resuing om emissions generaed by combusion of wase wood whichconains pains resins or preseraives re no we undersood The combusion of wase wood reaedwih chemicas may produce poeniay hazardous producs of incompee combusion (PIC) emissionssuch as dioxins• 2

Characerizaion of PIC emissions om he combusion of wase wood previousy reaed wih penachoropheno is repored in his sudy Uiiy poes nd crossbs are ypicay reaed wih a preseraive such as penachoropheno in order o proong heir serice ife They are disposed of byanding aer being aken ou of service Buing such wood wase in boiers for seam generaion

becomes increasingy aracive wase managemen aeaive as i conains subsania energy vauesand reduces anding coss Pioscae combusion ess were conduced under we conroedcondiions in a 058 2 miion Bur) combusor o compare PIC emissions om buingunreaed wood d penrachoropheno-reaed wood Sping and ayses for a wide vriey ofPICs incuding voaie orgnic compounds (VOCs) semivoaie organic compounds (SVOCs) ddioxins and rs were perfoned o assess he effec of penachoropheno preservaive presen inwood on PIC emissions

EXPEIMENTAL

Test Facility

The combusion esing was conduced using a muie combusor (MFC) insaed in heEnvironena Proecion Agency's research faciiy oaed a Research Triange Pk Norh CaroinaThe C shown in Figure 1 is a pioscae soker combusor wih 0.58 MW 2 miion Bhr)maximum hena oupu which is sufcien for simuaing he rnge of condiions ha migh beencounered in pracica sysems The C is capabe of buing a wide variey of soid es incudingmunicipa soid wase rese derived e biomass e and coa singy or in combinaion The

combusor is consruced wih moduar secions which provides maximum exibiiy for modiing hecombusor for research purposes Access pors are insaed hroughou he enire combusor for samping and visua observaion

The combusor was operaed in a spreader soker ring mode Wood e was sored i a arge rooffconainer ocaed near he buiding which houses he MFC A oe bin ed wih he wood e wasranspored o he MFC faciiy and he e was sequeniay dumped ino a oading hopper insaedouside he faciiy buiding using a forki A eecric drive conveyor be insaed under heoading hopper and peneraing hrough he faciiy buiding wa moved he e o a vibraing acive

PEERREVEW 8



sorage sio insaed inside he buiding The sio is designed for a 2 hour uover ime using anaverage e densiy of 80 kgm3 5 b/3) nd a feed rae of 163 kghr 360 bhr) The sio is argeenough o dpen ou effecs of spurious oading ye sma enough o inside he faciiy buiding vibraory sio is designed o improve mixing and reduce wa sicking The e ws disribued omhe sio ono an airigh horizona vibraory feeder conveyor conecing he sio o he ransiion secionof he spreader soker The mass ow of he conveyor was caibraed for conro of he e feed raeThe e raveed horizonay aong he conveyor and dropped hrough he ransiion secion ino he

feed injecion por0

he spreader soker The vibraory ransiion secion is designed wih an ine air penum area and adjusabe ine ange pae o faciiae spreading e ono he 6 1 by 30 cm 2 by 1)soker grae where a buing e bed is foed

Wood Fuel

Two differen wood es unreaed wood and reaed wood were obained om a pan where woodpoes are reaed wih penachoropheno The unreaed wood was pine poes ha are ypically reaedin he pan The reaed wood was a mixure of recenly reaed poes mosy sma pieces cu om heend o mee cusomers' engh specicaions and aged reaed poes aken ou of serice Boh reaed

nd unreaed poles were ground ino chips ess han 7.6 cm 3 in) in diameer The wo els werecharacerized by proximae uimae and chorine anayses: resus are shown in Tabe 1 can be seenha he reaed wood e is drier wih higher heaing value as compared o he unreaed wood Thechorine conen of he eaed wood e is 10 imes higher han ha of he unreaed wood

Combustion Test Parameters

The ony parameer invesigaed was he difference in emissions when buing reaed vs unreaedwood els under simir combusion condiions; no aemp was made o conduc prameric ess for his sudy In genera he operaing condiions of he es were considered opima when he e wasbuing a he designed hea reease rae wih nominay 160 excess air and a ow eve « 100 ppm) ofcrbon monoxide (CO) emissions in he ue gs

The moun of e bued was no measured coninuousy during a es was esimaed by weighinghe e before i was dumped ino he oading hopper of he MFC and measuring he ime required for is complee consumpion o cacuae an average feed rae The average feed rae was used o esimaehe amoun of e bued during a imed emissions smping period The MFC is equipped wihconinuous emission moniors (CEMs) for measuring oxygen (0 2) CO carbon dioxide (C0 2) nirogen

oxide (NO) sur dioxide (S0 2) oa hydrocarbon (THC) and hydrogen choride (HC) andequipmen for coninuousy monioring process emperaures d pressures

Sampling and Analytical Procedures

The emissions samping poin for he presen sudy was seeced a he duc which connecs heconvecive secion of he ace o he baghouse The seecion of a sampling poin prior o any gasceaning device was made o ensure ha any difference in ue gas poluan concenraions generaed bycombusion of reaed nd unreaed wood es woud be observed Emission measuremens made aer he ue gas ceaning device woud be expeced o mask his difference nd woud be reecive of heeeciveness of he devices (ie baghouse and causic scrubber) used

PEER-REVW 8



The samping program of the present study focused primariy on organic emissions particuary thosewhich are considered potentiay hazardous om the combustion of wood es. Smping andanaytica protocos used were based on existing PA methods for measuring organic constituents in uegases. Sampes for measuring voatie organic PIC emissions were taken using PA SW Method 000Voatie Organic Samping Train (VOST) and the voatie PICs in the VOST sampes were identiedand quantied using SW Methods 5040 and 8240. Sampes for measuring SVOC emissions wereobtained using SW Method 0010 and SVOCs in the sampes were anayzed using SW Method 820B.

Method 2 was used for measuring dioxin and ran emissions.8

SULTS AND DISCUSSION

Test Condtons

Six combustion tests three tests each for both the untreated and the treated wood es were perfoedunder simiar combustor operating conditions The untreated wood tests were performed rst foowedby the treated wood tests to avoid cross contamination. Tripicate runs were made to determine

experimenta repeatabiity. Since it was not practica to measure e feed rate continuousy the testswere performed under constant excess air eve (nominay 160 excess air) and a constt combustiongas temperature 850 C) measured by a thermocoupe ocated 152 cm 60 in) above the grate. Theestimated heat reease rates for a the tests are shown in Tabe 2 nd the average CMsmeasuredemission rates are shown in Tabe . The heat reease rates are cacuated based on the average e feedrate estimated by the amount of e consumed during the test period and the heating vaue of the emeasured experimentay It can be seen om Tabe 2 that the cacuated heat reease rates and themeasured ue gas ow rates for Untreated Tests 2 and re ower than those of the other tests. Theower ue gas ows for Untreated Tests 2 and are consistent with their ow e feed rates The heat

reease rate was set at 80 of the maximum designed output ofthe C for the present study. The efeed rate was adjusted manuay throughout a tests in order to maintain a constant temperature of 850C above the stoker grate and keep CO emissions beow 100 ppm which were considered optimumconditions for the tests. The combustion gas temperature measured may not have been aways truyrepresentative The tremendous turbuence generated above a buing hot e bed when the codunderre air passing through the grate and the cod overre air injected into the ace above the gratemay create a nonuniform gas temperature proe Observations through instaed viewing portsindicated that turbuent ow passed aong the entire ace during the tests. The heating vauesmeasured om the two e sampes may not be truy representative due to the nonhomogeneous natureof the wood es. These two uncertainties may have contributed to the ower estimated heat reease

rates for the two tests.

It was dicut to produce exacty identica combustion conditions for a the tests mainy due to the factthat the two wood es are not homogeneous. The treated wood e contains aged wood which isdrier and has 0 higher heating vaue than the untreated wood e Uneven e feed rates resutingom the fairy equent manua adjustment of the e feeder coud have caused uctuations in airtoe ratio and momentry excursions of CO emissions CEM data for CO and CO 2 and visuaobserations of e ow into the stoker suggest that sma excursions occurred during the tests. Thenonhomogeneous nature of the es couped with the practica dicuties to bu such es under we

PEER-REVEW 8



dd ondiion mak h aura imaion o ha rl ra durin impoil. Th hih CO miion hown in Tal 3, alulad ar h unrad wood ar anohr indiaion ha omuion ondiion wr diul o onrol whn uin h unrad wood whih ha low hain valu and hih moiur onn.

Pentachloropheno Desrucion Efciency

Th onnraion opnahlorophnol in h rad wood l wa analyzd o 4 100 mk ppmw. or h ix pnahlorophnol wa no dd in any o h mivolail orani mpl. Th imad pnahlorophnol druion iny (D) or ah ha n onrvaivly alulad ad on h pnahlorophnol analyi praial quaniaion limi Q.D rul ar prnd in Tal 4. Th Q i ad on h low aliraion onnraion and do no inlud aor uh a prn rovry or marix I i vidn om h rul ha uin o h pnahlorophnolrad wa wood in a okr omuor droy h pnahlorophnol inly wih a D hihr han ha rquird or hzardou wa druion 99.99.

Volaile Organic Compound (VOC) Emissions

Analy wr prormd or 50 VOC in ah o h ampl. Th VOC miion rul prnd in Tal 5 ar h ompound ound in onnraion hihr han h analyial dion limi in a la on . Hihr lvl o nzn wr ound in h unrad wood ampl whil romomhan wa ound a hihr lvl in h rad wood ampl Chloromhan 1,3-uadin iodomhan aon hloroorm and 12dihlorohan wr ound in oh unrad and rad wood ampl. Th ra lvl o hlorinad VOC miion ound in h unrad wood may poily aud y mall amoun o naurally ourrin hlorin in unrad wood.

or hlorinad VOC wr ound in h rad wood proaly a a rul o hihr hlorin onn in h pnahlorophnolrad wood.

SVOC EmissionsO h 8 mivolail orani ompound or whih aly wr prormd in h SY�C ampl only h ollowin v ard ompound wr ound o aov h analyial dion limiphnol aophnon naphhaln 2nirophnol and phnanhrn. Th oal SY�C miion ra or all ix i alulad y addin all h quanial SY�C miion in h and rul ar ummarizd in Tal 6. Th ypially low S�C miion or oh h unrad and rad wood

ar an indiaion ha ood omuion ondiion wr ahivd durin h . Th lihly lowr S�C miion or h rad wood ompard o ho or h unrad wood alo u ha h omuion o h drir rad wood l produd lowr IC. or moiur rlad durin h omuion o h "rn unrad wood l may lowr h loalizd omuion zon mpraur and au mor IC ormaion.

DioxinFuran (CDD/PCDF) Emissions

Th dioxinran ampl maurd y hod 2 wr n a h xi o h onviv ha xhanr and or h ahou. Th mpraur o h u a a h amplin poin wa wn 150 and 160 C I ha n hown ha h dioxin and ran ormaion "mpraur window in u

PEER-REVEW 8



a i wn 200 and 450 C I i raonal o xp ha h formaion of dioxin and ran ha alrady n ompld for h amplin loaion.

A hown in Tal oal CDDCD miion om h unrad wood [uin h Inaional Toxi uivalny ITQ mod of aounin for diffrn oxiii of CDDCD onnr] avrad 024 n ITQdm nd om rad wood 1.190 n ITQdm. Th miion ra ar prior o any onrol dvi ariula onrol dvi ould ponially rmov par

of hi marial om h a ram dpndin on h y ah ollion iny CDDCD formaion and olid-o-vaporpha pariion wih h dvi. Sin h mpraur a h amplin poin i low 160 C i i likly ha h ra of formaion and dorpion of yahaoiad CDDCD in a uun pariula ollion dvi would low. Th CD miion r inianly rar han CDD miion for oh h unrad and rad wood indiain d novo ynhi formaion raion rahr h ondnaion raion.II Th CDDCD onnr diriuion for h rad and unrad alo diffr. In h unrad wood h diriuion i pakd a h h lowr-hlorinad raCDD d diCD onnr; in h rad wood h diriuion i hid o h hihrhlorinad hxa-CDD and pnaCD onnr Th

CDDCD miion ra maurd om oh h unrad and rad wood ar onidrd low whn ompard o h ak miion om omrial muniipal wa omuor whih ran om 0.0 o 400 n ITQdm Th low CDDCD miion maurd om h unrad wood ar imilar o ho om uin naural wood whih ran om 0.066 o 0.2 14 n ITQdmTh CDDCD miion om h rad wood ar hihr han ho 0059 n ITQdm om a waonry plan uin a mixur of lan wood and pnahlorophnolrad wa wood

Th hihr CDDCD miion om h rad wood ompard o ho om h unrad

wood ar onin wih hir hihr hlorinad VOC miion Approximaly 200 ppm ofCwa murd in miion om h rad wood whil C wa no dd in h unrad wood . Th CDDCD ampl wr olld ino on half and ak half of h amplin rain and analyzd paraly whih iv an indiaion of h CDDCD aoiad wih h pariula marial and a aou miion Tal 8 how ha h prna of CDDCD in h on half ah i rar in h rad wood h in h unrad wood . Th rad wood had a hihr u a ow ra Tal 2 a a rul of h hihr hain valu of h rad wood ud whih would nan pariula load a h amplin poin Thi informaion u ha pariula arryovr may aff h oal amoun of CDDCD pially in h rad wood ampl whr a larr prna i in h on half ah. Comuor oprain ondiion in addiion o h wood ramn may alo onriu o hihr maurd CDDCD miion for h rad wood

COCLUSIOS

Thi udy wa ondud o idni ponial air miion prolm aoiad wih h omuion of wa wood primarily uiliy pol rad wih pnahlorophnol prrvaiv a a l for nry produion in a oilr. Th mphai of h udy wa plad on h hararizaion of h IC miion om omuion of pnahlorophnolrad wa wood. Th mhodoloy ud wa a

omparaiv of miion prior o h air polluion onrol dvi of a piloal omuor uin

EER-REVEW 84



unrad wood and wood rad wh pnahlorophnol prrvav a a l. Th howd ha omuon o pnahlorophnolrad wood an v mhod o droyn h pnahlorophnol onand n h wood wh druon n hhr han 9999 .

Drn n VOC SY�C d CDDCD mon om h omuon o unrad and rad wood l hav n nod. Th daa do no nal dnaon o h xa au o h drn

n mon. Th drn poly aud y h nanly drn mour onn

han valu and hlorn onn o h wo l. Th drn n u a ow ra rqurd or h omuon o h wo l wh drn omuon harar mour onn and han valu may alo au h drn n CDDCD mon Th mon ar rprnav only o h aly and onuraon d may no quanavly omparal o ohr omuor.

PRRVW 815



REFERENCES

. Shaowi B. G. Band Ga . Shlump Buhl . Hal and T. Nuaum "ioxin miion om Wood Comuion r 29 9 200 994.

2. Salh am T. H. Klipp . . k and . aky "omaion o olyhloinad ino-pdioxin C and olyhloinad inoan C uin h Comuion o Impnad WoodCrop, 30 : 20 99

3. A SW hod 0030 "Volail Oan Samplin Tain T hod o valuain Solid Wa A SW 846 NTIS B88-239223 nvionmnal oion Any O o Solid Wa Wahinon C Spm 986.

4. A SW hod 040 "oool o Analyi o Son Caid om Volail Oan Samplin Tain T hod o valuain Solid Wa A SW 846 NTIS B88239223 nvionmnal oion Any O o Solid Wa Wahinon C Spm 986.

. A SW hod 8240 "Ga Chomaoaphya Spomy o Oani Volail T hod

o valuain Solid Wa A SW 846 NTIS B88239223 nvionmnal oion Any O o Solid Wa Wahinon C Spm 986.

6. A SW hod 000 "odid hod Samplin Tain T hod o valuain Solid Wa A SW 846 NTIS B88239223 nvionmnal oion Any O o Solid Wa Wahnon C Spm 986

A SW hod 820B "Ga Chomaoaphya Spomy o Smivolail Oan Capllay Column Thniu T hod o valuain Solid Wa A SW 846 NTIS B88239223 nvionmnal oion Any O o Solid Wa Wahinon C Novm 990.

8. A hod 23 "minaion o olyhloinad ino-pdioxin and olyhloinad inoan om Saionay Sou Cod o dal ulaion Til 40 a 60 Appndix A U.S.Govn inin O Wahinon C 99.

9. Vo H. and Sili "Thmal Bhavio o CC in ly Ah om IninaoChmoph 9 986

0. U.S. A uniipal Wa Comuo Bakound Inomaion o opod Sandad o-omuion Thnoloy oman Vol. 3 A40389-2 NTIS B90486 U.S A

O o Ai Qualiy lannin & Sandad ah Tianl ak NC Spm 989

. Addink . and K. Oli hanm o omaion and uion o olyhloinad ino-p-dioxin and inoan in Honou Sym nvionmnal Sin and Thnoloy 29 4243 99.

2. Kilo J. . "Conol o ioxin uan and uy miion om unipal Wa ComuoJ oHsMa, 4 63 996.

3. ipinki G. "Tial Bu po and mi Appliaion Vikin ny o Bain I Sumid o

ihian pamn o Naual ou anin I July 4 99.

PEER-REVEW 6



�

.

Ash

Figure 1

Radiant FurnceI Coolg Wter

1=Covectve Secton

r Ash

Shemi of he muie ombuor

SmpligPort

,

tack

Ash Scrubber



Table 1 Charateristis of wood uels.

Constituent Content

Untreated Wood reated Wood

Proximate Ana�sisMoisture % 33.44 2 1.46

Ash % 0.25 0.57

Voatile Matter % 57.92 66.28

Fixed Carbon % 8.39 11.69

Heating Vaue kJ/g (Btu/lb) 12.953 (5569) 16.833 (7237)

Ultimate Anal�sisCarbon % 3383 43.24

Hydrogen % 4.20 4.92

Nitrogen % 0.28 0.28

Sulfur % 0.01 0.05

Oxygen % 27.99 29.48

Chlorine Anal�sisPentahloropheno ppm 6.7 4 100

24-dihloropheno ppm 2.4 3.6

Chlorine % 0.02 0.20

a: Measured on as-reeived basis

Tabe 2. Combustor operating onditions.

Test Averaged Fue Feed Rate Combustor Thermal Output Flue Gas Flow kgh bh) M (million B dsm

Untreated 134.4 (296.4) 0.48 (.65) 9.4

Untreated 2 17.1 (258.) 0.42 ( 1.44) 16.6

Untreated 3 1 14. 1 (25.6) 0.41 ( .40) 17.9

Treated 1 100.6 (22.8) 0.47 ( 1.6 1) 25.0

Treated 2 102.3 (225.6) 0.48 ( 1.63) 2.0

Treated 3 102.5 (225.9) 0.48 ( 1.63) 25.8

88



ble 3. Smmry of e g tempertre nd CEM dt

Lotion

Untreted • et 1

Stoker Setion Exit 849

Smpling Port 152

Contitent

12.5

CO 7.5

HO 11.0

203

N 103

TH 77

HCl < 1

S 10

in ppm @ 7%

Untreted

et 2

801

153

132

7 . 2

9 8

249

133

56

<1

1 1

emptue °

Untreted reted

et 3 et 1

827 869

153 155

Conenttion %

129 13.1

7. 1 6.7

9. 8 8.7

456 66

83 295

2 4

<1 195

13 <1

be 4 Detrtion efieny for penthloropheno

et DRE %

reted et 1 >99.9974 reted et 2 >99.9976

reted et 3 >999975

9

reted reted

Tet 2 et 3

92 1 870

160 160

13.3 13.3

6.5 6.5

8.7 9.0

2 1 20

178 2 10

3 3

194 183

< 1 < 1



Table 5.

VOCs

Chloromethne

1,3-Butadiene

Bromomethane

Iodomethane

Acetone

Chloroform

VOC emission rates

Untreated

Test 1

533

06

17

08

11.6

0.912Dichoroethane 1.3

Benne 254

Table 6. SVOC emission rates

Emission Rate dscm @ 7% 02

Untreated

Test 2

285

0.2

14

2.4

7.2

0.35.2

162

Untreated

Test 3

169

12

2. 1

5.7

7.5

030. 1

279

Treated

Test 1

558

0 1

154

17

45

26 16

2 1

Test Total Ession Rate. dscm @ 7% 02

Untreated Test 1 101

Untreated Test 2 11.4

Untreated Test 3 11.7

Treated Test 1 7.0

Treated Test 2 77

Treated Test 3 59

8

.

Treated

Test 2

967

0 1

33.9

5 1

117

1807

26

Treated

Test 3

515

0 1

705

241

14.3

3.9 29

30



Table 7 Total PCDDPCDF emission rates.

Test Emission Rate

Total PCDD, Total PCDF, Total PCDDPCDF, Total PCDDPCDF,ndscm ndm ndscm ng I-TEQ/dscm

ntreated Test 8.4 22.3 30.7 0.5

ntreated Test 2 2.6 17.2 19.8 0.2

ntreated Test 3 1.0 . 2. 0 1

Treated Test 15.0 422 572 13

Treated Test 2 20.9 56.5 77.4 12

Treated Test 3 18.7 45.0 63.7

: @ 7%

Tabe 8 Distribution oPCDDPCDF in sampling train

Test % oPCDD I-TEQ % oPCDF I-TEQin Front Hal in Front Hal

ntreated Test 31.6 24.1

ntreated Test 2 53.0 40.1

ntreated Test 3 49.0 33.3

Treated Test 758 634

Treated Test 2 704 59.4

Treated Test 3 680 59.7

821

characterization of pic emission from comb of pentanchlorophenol

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