Organic compounds in the waste gasification and combustion process

Chemosphere, Vol.25, No.4, pp 437-447, 1992 Printed in Great Britain

0045-6535/92 $5.00 + 0.00 Pergamon Press Ltd.

ORGANIC COMPOUNDS IN THE WASTE GASIFICATION AND COMBUSTION PROCESS

J. Wienecke, H. Kruse and O. Wassermann

Department of Toxicology, Christian Albrecht University D-2300 Kiel, Germany

(Received in G e r m a n y 19 June 1992; accepted 9 July 1992)

Abstract

This study deals with the identification and quantification of organic compounds in a pilot plant for waste gasification and combustion at different sampling points. The samples were taken after the gasifier, after the gas purifier and after combustion. Organic compounds including polycyclic and heterocyclic aromatics, phthalate esters, halogenated benzenes, biphenyls, naphtlialenes, phenols as well as nitrocompounds were separated by capillary gaschromatography and quantified by mass spectroscopy. Keywords Waste gasification, combustion, organic compounds, resyathesis, halogenated aromatics and nitroaromatics, PVC, polyester, GC-MS. Introduction

Since the first publication of erie et al. (1) on the formation of polyehlorinated dlbenzodloxins by waste incineration the oeeurence and the formation of polychlorinated dibenzodioxius and -furaus (PCDD/F's) are described in many studies. The PCDD/F's can be derived from precursors like polychlorinated phenols, polychlorinated plienoxyphenols and polychlorinated biphenyls or from unrelated compounds llke hexachlorobutadiene (2-5). The surface catalyzed reactions occur principally in cold zones on fly ash particles (2,6), but there is also the possibility of homogenous gas phase formation of PCDD's from chlorophenols via phenoxy radicals (7.8). Polyeyclic aromatic compounds like naphthalene are adsorbed on fly ash, where in the presence of gaseous HCI or HBr chloro/bromo substituted naphthalenes are generated (9). The de hove synthesis from particulate carbon in presence of inorganic chloride (activated by copper ions (10)) is besides PCDD/F's possible with other compounds such as polychlorobenzenes, polyehlorinated naphthalenes and biphenyls (11) or polychlorinated pyddins, anilines, benzophenones, 9-H-xanthene-9-ones, benzouitriles and fluorenones (12). Further organic compounds were detected in fly ash (13, 14) and flue gas (15) from municipal incinerators. In this study the combustion products of the "Lurgi Eco Gas Procedure" (16) are analysed, where the waste is gasified and the purified gas is introduced into the Circulating Fluid Bed (CFB) reactor of the power station for energy production. In two different tests standard waste was spiked with PVC and polyester, respectively. A wide variety of organic compounds has been characterized in the emissions of this pilot plant, and the dependence of their formation both on system temperatures and waste composition has been studied. Because of the presence of ammonia and nitrogen, nitro derivatives have also been identified. 437

438

Materials and methods

The sorted waste (aboute 400-500 kg/hour) was gasified under deficient oxygen conditions in a reactor, G, with coupled cyclones, C1, C 2 (see figure 1). After the second cyclone, (]2, the first samples were taken at PI' at a temperature between 850-1 000 *C. This crude gas ("raw gas" or "processing gas" after gasifier) streams through a gas purifier, which consists of a quencher, Q, cooling the gas from 800 °C down to 400 *C., a cyclon, C3, a radial flow scrubber, RS, for precipitation of dust and wash-out of HC1 and NH3, and a tube cooler, R, where the gas is cooled down to 60 °C. The samples were taken at P2. This purified gas passes the combustion chamber at a temperature of about 850 *C (residence time: 2-3 s). The combustion chamber can be substituted by a CFB-reactor. The third samples (flue gas) were taken at the outlet of the stack at P3. The samples taken at P1 and P2 demonstrate the situation in the pilot plant, only.

f

uNR

m

P3

G

)

()B0 ~2

#C)

Figure 1: Pilot plant for waste gasification and combustion. G gasifier (height 10 m, inner diameter 0.7 m), C , C cyclones, purifier equipment; Inset: details of gas purifying installation: Q quencher, C 3 cyclone, RS radial flow scrubber, R tube cooler, Bm blower, C5 combustion chamber, St stack, P1, 2, 3 sampling points.

In practice, sampling of stack emissions usually is not performed under strictly isokinetic conditions, but in this study the volume flow fractions taken were identical (17). The samples were taken under different test conditions: In tests 1 and 2 the input was average m'anicipal waste. In test 3 the input was spiked with PVC (4 weight percent), and in test 4, with polyester (6 weight percent). In tests 2, 3 and 4 oxygen was added to enrich the air for the gasification, and it was fed through the nozzle grate. In test 1 40 % of oxygen passed through the grate, and 60 % were added with lances at three points, two in the fluidized bed and one in the cyclone area. The oxygen concentrations in the pilot plant are measured after gasification (Table 1): Table 1:

Oxygen concentrations measured in the pilot plant O z [vol. %]

test 1 after purifier test 2 after purifier test 3 with PVC addition after purifier test 4 with polyester addition after purifier test 1 after combustion test 2 after combustion

7 7 10 9 9 10

439

Both in crndc and purified gas the concentrations of hydrochloric acid and of ammonia were determined (Table 2): Tsbte Z. Concentrations

of HCI and NH 3 in crude gas and purified gas

crude gas pm,'ified gas

HC! [mg/Nm~]

NH3 [mg/Nm3]

1 500 - 2 000 15 - 40

2 000 - 2 500 100 - 200

The sampling system consisted of a quartz probe with two washing bottles, (each containing 50 ml ice-cooled nonane, Fluka) and a membrane pump with a flow of 2 to 3 l/min, and a gas meter. At P1 dust was separated by a quartz wool filter at 850°C. At the other points the sample was taken without filtering because of the very low concentration of particles. It should be noted, that from the total combustion products the nonane soluble fraction could be trapped only. Due to shielding effects of the solvents, volatile compounds of low molecular weight, like acrylonitrile and hydrazlne, both characteristic for waste inoineration emissions, cannot be detected using this sampling method. The corresponding gas volumes, calculated under normal conditions, are given in table 3. Table 3:.Gas volumeS passed through I00 ml nonane, calculated under normal conditions

sample

gas volume [NL]

test 1 test 2 test 3 (addition of PVC) test 4 (addition of polyester)

Pl

P2

P3

92 72

615 655 155 888

691 708

1, 3, 5 Triphenylbanzene was added to each sample as internal standard. The allquotes were submitted to the GC-MS analysis. No impurities were found in the blank of nonane. In order to lower the detection limit the samples were reduced to about 1 ml under a gentle stream of high purity nitrogen, then transferred into a i ml reacti vial, evaporated to dryness and redissolved in a defined volume of n-hexane (concentration factor 1: 100). The leakage due to evaporation of the compounds investigated is estimated to less than 20 percent. For analysis of the PCDD/F's the samples were cleaned up according to Ball et al.(18) and Smith et al. (19) The GC-MS system used was a Finnigun 5100. Table 4:.

Conditions of GC-MS analysis

Colunm: Temperature: Injection: Injector and Interface Temperature: Ion source Temperature: Cartier gas: Mass spectrometer: Multiplier voltage: Eleetron energy: Measuring modus:

Fused silica capillary colunm, DB-5, 0.25 m x 60 m 60°C for 3rain + 10 °C/rain to260 ° + 260°C for 47rain Splitless mode 250 °C 160 °C Helium, 5.5 ml/min quadropole system 1300V 70 eV EI

The polyaromatics, heterocycles and phthalatc esters were identified using the full scan modus. The polyhalogenated and nitro compounds were identified by the selected ion monitoring (SIM) on the basis of three characteristic masses. The structure of an nnknoWn compound is described in three steps: comparison of the retention time with that of reference compounds, comparison of the fragment pattern of the unknown compound with the library entries, comparison of the fragment patterns of the reference substance and the explication of the mass fragments by possible structures, or the comparison of the relative intensity ratio of three characteristic masses with reference compounds. The accepted deviation of the retention times from the reference substance was _-. 10 s, and the accepted retention time differences of peaks in SIM presentation were -+ 1 s. The various ions monitored are listed in table 5.

440

Table 5:

Characteristic ions monitored during selected ion monitoring analysis

Substance and Compound Class

ion (m/e)

Chlorobenzenes 1. Dichlorobenzenes 2. Triehlorobenzenes 3. Tetraehlorobenzenes 4. Pentaehlorobenzenes 5. Hexaehlorobenzene 6. Chlorostyrene

111.0 180.0 213.9 247.9 281.8 103.0

146.0 182.0 215.9 249.9 283"8 138.0

148.0 184.0 217.9 251.9 285.8 140.0

Chlorophenols 1. Dichlorophenols 2. Trichlorophenols 3. Tetrachlorophenols 4. Pentachlorophenols CMoro, bromophenols

63.0 196.0 229.9 263.9 206.0

162.0 198.0 231.9 265.9 208.0

164.0 200.0 233.9 267.9 210.0

CMoronaphthalenes 1. Chloronaphthalenes 2. Dichloronaphthalenes 4. TetracMoronaphthalenes 5. Oetaehloronaphthaleoes

127.0 126.0 263.9 401.8

162.0 196.0 265.9 403.8

164.0 198.0 267.9 405.8

Chlorodibenzodiozdns 1. Tetrachlorodioxins 2. Pentaehlorodioxins 3. Hexaehlorodioxins

319.9 353.9 387.8

321.9 355.9 389.8

323.9 357.9 391.8

Chlorodibenzofurans 1. Tetrachlorofurans 2. Pentaehlorofurans 3. Hexaehlorofurans

303.9 337.9 371.8

305.9 339.9 373.8

307.9 341.9 375.8

Chlorobiphenyls 1. Trichlorobiphenyls 2. Tetraehlorobiphenyls 4. Pentachlorobiphenyls 5. Hexachlorobiphenyls 6. Heptachlorobiphenyls 7. Octachlorobiphenyls 8. Nonachlorobiphenyls 9. Decachlorobiphenyls

186.0 289.9 323.9 357.8 391.8 427.8 461.8 495.8

256.0 291.9 325.9 359.8 393,8 429,8 46.3,8 497.8

258.0 293.9 327.9 361.8 395.8 431.8 465.8 499.8

Chloroheterocycles 1. Tetrachlorothiophene 2. Dichloroquinolines

219.9 162.0

221.9 197.0

223.9 199.0

Unsaturated Organochlorine 1. Hexachlorobutadiene

222.8

224.8

226.8

Nitrocompounds 1. Dinitrobiphenyis 2. Dinitronaphthalenes 3. Nitropyrenes

139.0 114.0 189.0

168.0 12/i.0 201.0

198.0 218.0 247.0

The ranges of mass deviation were selected to ± 0,25 mass units. The most intensive fragments [relative intensity: 100 percent) are set in bold.

441

The quantification is performed by external calibration with standards. Quantitative determination of the polyhalogenated compounds based on comparison of peak areas of mass fragmentograms for (M + 2) + ion or of a specific degree of chlorination and the corresponding (M + 2) + ion of the reference compound. The other compounds were determined by peak areas of molecular peaks or the most intensive fragments. The selected peak areas of the reference compounds were in the same proportions as the substances of unknown concentration, and the errors of determination amount to about -+ 10 %. The detection limit under consideration of the concentration factors amounts to 2-20 ~1g/Nm3 in the full scan modus (injection volume: 1 1~1) and 1-150 ng/Nm3 in the SIM-modns (injection volume: 1 1~1), (lowest reference value: dicMorobenzene; highest reference value: dinitrobiphenyl). Results and discussion The investigation with the total ion current trace (TIC) shows polycyelic and heterocyclic aromatics as well as a number of uncharacterized hydrocarbons, aliphatie esters and ketones, nitrogen and sulphur containing heterocyclic substances. Their identification hitherto is uncertain, because no reference substances were available and the structure assumption based only on mass spectroscopy data. Chloro- and bromododecane have been detected in SIM, their identification was impeded by the presence of various hydrocarbons. All substances presented in this paper are well explained by reference compounds. Figure 2 shows a GC-MS chromatogram of a flue gas sample in TIC presentation.

N*phl~*,*n°

I

Figure 2. TIC presentationof a concentratedfluegas sample(test 1)

In every sample naphthalene was the most prominent compound followed by other polycyclic aromatics such as biphenyl, anthracene and heterocycllc aromatics like benzothiopheue and dibenzofuran. In some samples of the purified gas the polyhalogenated benzenes, bipheuyls, naphthaleues and heterocycles are detected even in the less sensitive full scan modus. Figure 3 shows the mass fragmentograms of chloro-and dichloronaphthalenes detected in the full scan modus.

442

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i~O_ .................

I r

I~l ~ .,ll: - , :

,~

'

I ,~,i,~LJ,,,LL Jl .............l.................I~...........................

'

,

...: : ~-

; . .~,...,..

~

..'

.

.z

'

I

J,,i~[,kL_J~k.~,

Figure ~.. Mass fragmentogram of cMoro- and dichloronaphthalene

i~.h .............

I ................

P]'gure 4:. Mass fragmentogramm of dichlorobenzene (test 4) and tetrachlorothiophene (test 4)

of test 4

j, , * -...°?_ ° ..........

za.

~.L" ~ mz4

-

"

' 1~,~

Figure ~.. S I M of tetrachlorothiophene (test 2, sample

IT:L9 T~

P 3)

Figure 6: SIM of dichloroquinolin¢ (test 1, sample,

P 3)

Figure 4 shows the mass fragmentograms of diclalorobenzene and tetrachlorothioplaene in the full scan modus and Figure 5 shows tetracblorotbiophene of a flue gas sample in the SIM-modus. In this study diehloroquinoline is only presented in the SIM-modus (Figure 6) by three ion current traces with the characteristic masses 162, 197, 199 (m/e = 197, 199 chlorine cluster; m/e = 162 the splitt off of the first chlorine). The compounds analysed are listed in table 6. The values of the combustion products from the standard waste are presented for the crude gas (samples P1) of test 1 and test 2 of investigation at P1, the purified gas (samples P2) at P2 and the flue gas (samples P3) at P3. For comparison, the purified gas samples after addition of PVC (test 3) and of polyester (test 4) are presented in table 6. In this study no individual isomers are analyzed. Not all isomers of reference substances are commercially available, and the high resolution structure analysis on the basis of mass spectroscopy data is not possible.

3 800 n.d. n.d. 1 900 2 400 n.d.

3 145 n.d. 410

Dinitrobiphenyl Dinitronaphthalene Naphthalene carbonitril Nitropyrene

8 85 n.d. 5 400

71 000 35 n.d. 5 600 12 000 14

75 000 14 19 90 000 n.d. n.d. n.d. n.d. n.d. 66 000 n.d. n.d. 5 000 24 240 86 23 500 5 900 290 110 760 77 000 90 1 000 000 n.d. 7 1(30 n.d. 9 000 40 000 750

Anthracene 29 000 Azulene 5 Acenaphthene 150 Acenaphthylene 8 500 Benzofluorene 530 Benzofluoranthene n.d. Beazoperytene n.d. Benzo(a)pyrene 1 100 Benzacephenantrytene 1 100 Biphenyl 10 000 Biphenylene 800 Binaphthalene n.d. Chrysene 750 4H Cyclopentaphenanthrene n.d. Dihydroanthracene 105 Ethenyhaaphthalene 35 Fluroranthene 5 300 9H Fluorene 2 000 9H Flurorenone n.d. Methylanthracene 18 Methylbiphenyl 2 900 Methylnaphthalene 21 500 Methylphenanthrene 18 Naphthalene 315 000 Naphthalene carboxyl aldehyde n.d. Phenanthrene 1 100 Phenylanthracene n.d. Phenylnaphthalene 1 900 Pyrene 4 100 Trlphenylene 3 000

Benzothiophene Benzonaphthothiophene Quinoline Dibenzofuran Dibenzothiophene Methylbenzothiophene

Test 2

Test I

samples P1

11 n.d. n.d. 40

12 000 n.d. 33 3 000 780 n.d.

4 100 22 100 14 000 5 15 12 30 50 17 000 330 14 860 n.d. 140 520 510 2 200 38 26 40 14 300 40 270 000 n.d. 3 400 rod. 290 950 90

Test I

Test 2

4 100 n.d. 8 2 700 n.d. n.d. n.d. n.d. n.d. 2 300 5 n.d. n.d. n.d. n.d. 60 62 310 n.d. 26 108 1 600 40 35 000 135 115 n.d. 150 400 n.d.

2 000 n.d. n.d. 300 300 n.d.

11 40 n.d. 170

2 20 n.d. 4

Nitrogen compounds [ g/Nm~]

56 000 n.d. n.d. 2 700 730 14

Heterocyclie compounds [ g/Nm~]

3 900 31 50 13 500 n.d. n.d. 5 n.d. n.d. 43 000 75 n.d. 110 n.d. 840 75 1 300 1 200 160 37 1 250 54 000 3 54 000 82 250 n.d. 570 2 100 25

2 4 n.d. 4

800 n.d. n.d. 450 n.d. n.d.

1 000 n.d. n.d. 130 n.d. n.d. n.d. n.d. n.d. 1 000 n.d. n.d. 7 n.d. n.d. n.d. 54 n.d. n.d. n.d. n.d. 760 n.d. 23 000 n.d. n.d. n.d. n.d. 5 7

samples P3 (Emission) Test I Test 2

Polyaromatic compounds [ g/Nmj]

samples P2

720 n.d. 480 160

208 000 740 800 12 000 2 600 n.d.

550 000 6 300 8 700 18 000 57 000 n.d. n.d. 9 700 n.d. 92 000 130 0(30 450 2 500 47 000 700 100 000 28 000 59 000 25 n.d. 70 1 200 n.d. 2 300 0(30 n.d. 27 600 500 20 000 59 000 17 300

360 1 400 1 700 54

88 000 n.d. n.d. 5 000 550 740

154 000 n.d. 2 200 29 800 410 n.d. n.d. 2 200 n.d. 320 000 8 000 n.d. 2 100 4 000 n.d. 6 000 3 500 10 200 230 150 200 11 900 150 2 000 000 80 n.d. 20 800 3 700 1 000

sample P2 sample P2 Test 3(PVC) Test 4(Polyester)

Table 6: Compounds identified by GC-MS of waste gasification and combustion of a pilot plant. Individual isomers of the compounds are not identified.

compound

4~

continue table 6

1 500 3 800 34 000 n.d.

1 600 51 200 1 200 10 400 n.d. n.d. n.d. n.d. 11 000 430

Chloronaphthalenes Dichloronaphthalene Tetrachloronaphthalene Octachlor onaphthalene

Trichlorobiphenyl Tetrachlorobiphenyl Pentachlorobiphenyl Hexachlorobiphenyl Heptachlorobiphenyl Octachlorobiphenyl Nonachlorobiphenyl Decachlorobiphenyl

Dichchloroquinoline Tetrachlorothiophene 140

225 000 n.d.

1 800 n.d. 220 n.d. n.d. nA n.d. n.d.

36 000 89 000 250 n.d.

10 000 5 700 12 000 29 000 100

12 000 2 700 980 800 n.d. 5 100 3700 430 270 170 430

740 160 54 n.d. 9

720 6 n.d.

25 n.d. n.d. n.d. n.d. n,d, n.d. n.d.

33 22300 390 31 2 000 n.d. n.d. n.d.

280

320

7

Halogenated unsaturated compound [ng/Nm 3] n.d.

600 570

25 n.d. n.d. n.d. n.d. n,d. n.d. n.d.

4 200

9 100

3 300 31 n.d.

Halogenated Biphenyls [ng/Nm j]

280 000 38 000 35 n.d.

Halogenated Naphthalenes [ng/Nm 3]

27 0013 2 300 3 600 n.d. 37

1 400 2 600 6 100 7 100 21

II000

5800 1 100 670 150 310

6 700

10000

Halogenatefl Phenols [ng/Nm3]

240000 66000 14 000 4 300 100 65 000

Halogenated Benzenes [ng/Nm ~]

Phthalate esters [ g/Nm~] 35 140 4 400 2 200

samples P3 (Emission) Test 1 Test 2

Halogenated heterocyclic compounds [ng/Nm3] 12 000 61 000 1 500 560 900 380

35 2 100 410 53 2 100 n.d~ n.d. n.d.

100 000 23 000 10 n.d.

22 000 1 700 3 700 32 000 700

43000 20000 6 800 2 100 32 8 800

140 4 100

samples P2 Test 1 Test 2

n.d. = not detectable; the concentration is under the detection limit or the identification is uncertain

22

3 400 5 0130 9 300 11 000 600

Dichlorophenol Trichlorophenol Tetrachlorophenol Pentachlorophenol Chloro, bromophenol

Hexachloro(1,3) butadiene

5 900 50 38 290 n.d. 1 200

Dichlorobenzene Trichiorobenzene Tetrachlorobenzene Pentachlorobenzene Hexachlorobenzene Chlorostyrene

Test 2

470 40 000

samples P1

240 36 000

Test 1

Diisobutylphthalate Diisooctylphthalate

compound

7500

11 000 13000

100 200 90 620 110 4 500 n.d. 1 300

2900000 160 000 6 500 700

110 000 270 000 860000 900 000 1003O

280000 310 000 130000 430000 70 000 3700000

380 700

6 400

210 000 2400000

70 400 1N) 160 670 2 200 380 2 700

1080000 190 000 4 500 20

230 500 570 000 98000 11 000 70

330000 1 900 000 1800000 800000 92000 2800000

35 20

sample t"2 sample t"2 Test 3(PVC) Test 4(Polyester)

445

The identified compounds are classified in polyaromatic and heterocyclic compounds, phthalate esters and nitrogen compounds, halogenated benzenes, phenols and naphthalenes. Many of these organic substances have been detected by Karasek et al. in fly ash samples from municipal incinerators with GC-MS and high performance liquid chromatography (HPLC) separation (13, 14). Some of these compounds were also detected in the flue gas of waste incineration emission by Bartelds et al. (15). The total concentration of the noahalogenated polycyclic compounds decreases continuously from crude gas to flue gas. No resynthesis effect is observable. The samples with PVC and polyester addition show about ten times higher concentrations than those of the standard waste. Figure 7 shows the total concentration of the nonhalogenated polyaromatic compounds from the crude, purified and flue gas of the first investigation day (test 1), in comparison to samples "after PVC and polyester spiking of the waste.

sN 4oe

ze¢, iJllNm~

140 rl

pa ~pllm

el

120

IltNm|

80

_

60

].s I

,~"

40 2,

zo

Ls i

~

~.

i,

PI p2

pvc

P2

~mpl~

PJ

PI

P2

P$

Cble~phemol.

P1

P2

P3

Chlo~n.pbthalene8

Samples

~*t~,

totalconcentrationof the nonhalogenatedpolyaromatic compoundsof test I samplesand the purifiedgassamples withPVCand polyesteraddition.Notethe changeof unit (mg/Nm3 and g/Nm3).

Figure ~ The

P2

Cb I o ~ b e m w n e |

............

Figure 8:. The sum of total concentration of hslogenated benzene,s phenols and naphthalenes in the first day sample (test 1)

The heterocyclic and nitrogen compounds show the same tendency. Diisobutylphthalate and diisooetylphthalate could be demonstrated as significant emittants. Thus waste incineration is one of the possible sources of the atmospheric ceneentration of dibutylphthalate (DBP) and bis-(2-ethylhexyl)-phthalate (DEHP), which are found in the Swedish atmosphere (20). The average fall-out rates at 14 localities in Sweden were determined as 16.8 k~g m "2 month"1 (DBP) and 23.81-1g m "2 month"1 (DEPH), and the total deposition to the ground in Sweden was estimated to 200 tons year "1. The halogenated compounds can be derived from the substitution reaction of biphenyl, quinoline, dibenzofuran and

naphthalene with chlorine and other halogens. The concentration of organic compounds incxeases with decreasing temperature, as demonstrated by the halogenated benzenes, phenols and naphthalenes (de novo synthesisor substitution reactionswith polyaromatic compounds). Figure 8 shows the totalconcentrationof halogenated benzcnes, phenols and naphthalencs in the firstday sample (testi). After combustion the concentrationof organic compounds decreases with increasingtemperature. With increasingdegree of chlorination, the concentrations of benzenes and naphthalenes are declining. The countercurrunt tendency ist represented by the halogenated phenols. Except the dichloro derivatives, the concentration of chlorinated phenols increases parallel to the degree of chlorination.

446

Figure 9 presents the concentrations of purified gas samples (P2) of test I in dependence on the degree of chlorination. Assnming electrophilic substitution reactions from inorganic chlorine with the aromatics, the high + M effect of the phenolic hydroxy group activating the reactivity would explain this phenomenon. Figure 10 shows the possible chlorination mechanism. The electrophilic aromatic substitution reactions are favoured in presence of l.z~wis catalysts, especially transition metals, which are selectively erroded from the fly ash surface (21).

iJs/Nm3 $0

40

,!

/

•

c,~c,~-~,.

.++ I0

0

~

!~!

/. . . . . " DI-

~,.

~~,

Trl-

Tetra- PeBnl. H n a -

~

i~ DI-

CI

~ Trl-

,~ Tetra- Penta-

CI.

CI

c,

c,"

-. Mz° C o t o l y s t

CI

degree of chlorination Chlorobenmne

Chlorophenol

Figure ~. Purified gas samples: halogenated benzenes and phenols of test 1 dependent on the degree of chlorination

Figure 1~. Electrophilic substitution of phenols with inorganic chlorine in presence of Lewis catalysts

Polychlorinated phenols are precursors for dioxin formation, and polychlorinated biphenyls are possible precursors for the furan synthesis. Tetra-, penta- and hexachlorodibenzodioxins and -furans were identified in some samples. However the sampling method applied by Lurgi AG impeded the quantification of PCDD/F's because of both very small gas volumes and the lack of spiking with 13 C labelled PCDD/F's as standards of recovery. Carcinogenic organic compounds, such as chrysene, hexachloro (1,3) butadiene, dinitronaphthalenes and nitropyrenes, are present in the emissions of waste combustion.

Conclusions

Polyaromatic and heteroeyclic compounds, phthalate esters and nitrogen derivatives, halogenated heteroeycles, benzenes, phenols, naphthalenes and biphenyls are present in emissions from waste gasification and combustion. In the presence of chlorine - and probably also of the other halogens - non halogenated polycyclic aromatics are transformed into halogenated derivatives possibly by electropkilic substitution. The addition of PVC and polyester to the waste tendentious augments the concentration of the investigated compounds. The emitted carcinogenic nitroaromatics deserve serious attention.

Acknowledgements We are grateful to Lurgi AG, Frankfurt a. M., Germany, for generous supply of waste gasification samples and for the financial support.

447

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