biomass and bioenergy 33 (2009) 933940

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Effect of pyrolysis temperature on the composition of the oils obtained from sewage sludge
ndezb, A. Domnguezb, J.J. Pisb, O. Martneza, L.F. Calvoa, P.L. M.E. Sancheza,*, J.A. Mene c Bernad
a

n, n, Natural Resources Institute, University of Leo Avda. de Portugal 41, 24071 Leo Spain n, Instituto Nacional del Carbo CSIC, Apartado 73, 33080 Oviedo, Spain c Department of Organic and Inorganic Chemistry, University of Oviedo, Oviedo, Spain
b

article info
Article history: Received 28 July 2006 Received in revised form 9 February 2009 Accepted 10 February 2009 Published online 5 March 2009 Keywords: GCMS Sewage sludge Oil composition Pyrolysis PAHs

abstract
Sewage sludge was pyrolysed in a quartz reactor at 350, 450, 550 and 950  C. The pyrolysis oils from the sewage sludge were characterized in detail by means of gas chromatography mass spectrometry (GCMS). Changes in the composition of the oils related to the process conditions were assessed by normalizing the areas of the peaks. It was demonstrated that, as the temperature of pyrolysis increased from 350 to 950  C, the concentration of monoaromatic hydrocarbons in the oils also increased. Conversely, phenol and its alkyl derivatives showed a strong decrease in their concentration as temperature rose. Polycyclic aromatic hydrocarbons (PAHs) with two to three rings passed through a maximum at a pyrolysis temperature of 450  C. PAHs with 45 rings also presented a major increase as temperature increased up to 450  C, the concentration at 950  C being slightly higher than that at 450  C. Quantication of the main compounds showed that sewage sludge pyrolysis oils contain signicant quantities of potentially high-value hydrocarbons such as monoaromatic hydrocarbons and phenolic compounds. The oils also contain substantial concentrations of PAHs, even at the lowest temperature of 350  C. The pathway to PAH formation is believed to be via the DielsAlder reaction and also via secondary reactions of oxygenated compounds such as phenols. 2009 Elsevier Ltd. All rights reserved.

1.

Introduction

The increasing amounts of sludge generated by wastewater treatment are a problem causing growing concern since they represent a potential risk to human health and the environment. Owing to more restrictive legislation on the discharge of residual waters, methods formerly used for their disposal [1] have become much less acceptable. Sewage sludge, like most organic wastes, is rich in volatile matter and can therefore be converted into a usable energy source. The recovery of energy from sewage sludge and solid

wastes has focused on thermo-chemical processes such as direct combustion [1], gasication [2,3] and pyrolysis [48]. Of these processes, pyrolysis has been receiving increasing attention in recent years as an acceptable route for waste disposal [9]. The main reason for this is that in the pyrolysis process the conditions can be optimised to maximize the production of either chars, oils or gases depending on the product required [1012]. In an earlier work on the pyrolysis of biomass [8], it was reported that high heating rates at temperatures around 500  C favour the formation of oils and minimize char and gas formation. High heating rates to

* Corresponding author. Tel.: 34 987291841; fax: 34 987291839. E-mail address: mesanm@unileon.es (M.E. Sanchez). 0961-9534/$ see front matter 2009 Elsevier Ltd. All rights reserved. doi:10.1016/j.biombioe.2009.02.002

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biomass and bioenergy 33 (2009) 933940

temperatures higher than 500  C tend to favour the formation of gases, whereas low heating rates at low temperatures maximize the yield of char. All pyrolysis products have a potential use. For example, char can be burnt as fuel or disposed off (since the heavy metals are xed inside the carbonaceous matrix), or it can even be upgraded to activated carbon [13]. Gas can be used as fuel [14], whereas oil can either serve as fuel or as a raw material for chemicals. Many works in the literature focus on the production of liquids from the pyrolysis of organic wastes such as tyres [15], wood, municipal solid waste, rice husks [16], biomass [17] and cellulose [18]. Pyrolysis oils derived from sewage sludge have also been analysed in several studies [1922]. Pyrolysis oils from sewage sludge have the potential to be used as a fuel oil substitute after upgrading or as a source of chemicals. In both cases, an in-depth knowledge of their composition is required. However information on the individual yields of the compounds and the inuence of the pyrolysis parameters on their concentrations is limited. An exhaustive qualitative and quantitative analysis of the oils was carried out by means of gas chromatographymass spectrometry (GCMS). Changes in composition of the oil relating to pyrolysis temperatures were assessed. Pyrolysis oils contain signicant quantities of potentially high-value hydrocarbons such as mono-aromatics and phenolic compounds. As the temperature of pyrolysis is increased the concentration of monoaromatic hydrocarbons in the oils also increases. Conversely, phenol and its alkyl derivatives show a strong decrease in their concentration with temperature. The oils also contain substantial concentrations of polycyclic aromatic hydrocarbons (PAHs).

Table 1 Selected chemical characteristics of the sewage sludge. Proximate analysis M

6.8

Va
59.2

Aa
32.4

FCa,b
8.4

Ultimate analysis Ca,c

55.27

Ha,c
7.78

Na,c
9.75

Sa,c
1.36

Ob
25.84

H/C
1.7

GCV (kJ kg1)

16,457

Composition of main inorganic elements (expressed as wt.% of metal oxidesa) Na2O

0.42

MgO Al2O3 CaO Fe2O3 K2O MnO SiO2 TiO2

1.49 7.34 5.29 2.98 0.97 0.05 18.9 0.36

M: moisture content; V: volatile matter content; A: ash content, FC: xed carbon, GCV: gross caloric value. a Dry base. b Calculated by difference. c Ash free basis.

2.
2.1.

Experimental
Sample

long and was constructed with quartz. A sample of sludge approximately 30 g in weight was placed in the centre of the hot zone of the reactor. In order to obtain an inert atmosphere, a helium (He) ow rate of 100 mL min1 was passed through the sample bed for 30 min prior to the commencement of the experiment. The He ow was shut down during the pyrolysis so that volatiles derived from the sample would have high residence times in the reactor and secondary reactions would be favoured. The sample was heated at a controlled rate of 30 K min1 from room temperature to a nal temperature of 350, 450, 550 and 950  C. Once the required temperature was reached, the system was allowed to cool outside the oven.

A representative sample of anaerobically stabilised sewage sludge from an urban wastewater treatment plant sited in Leon (in the North-West of Spain) was used in this work. This plant carries out an aerobic suspended-growth treatment process, and then it goes through a stabilization treatment by anaerobic digestion, dehydration and thermal drying. Despite that the representative sample used in this work was collected in autumn; it was observed that the characteristics of the sludge do not change too much with the season. The sludge was dried and crushed to a particle size of 2 3 mm. Table 1 summarizes the main chemical characteristics of the sludge. The volatile matter content (V) was calculated by heating the sample up to 900  C in the absence of oxygen, while the amount of ashes (A) was determined by burning the sample at 815  C in a mufe furnace fed with air. The moisture content (M) was around 7% by weight (wt.%) and the ash content was 32.4 wt.%. More than 50 wt.% of the dry sludge corresponded to the organic fraction, making it a valuable source of organic compounds when pyrolysed.

2.3.

Recovery and characterization of oils

2.2.

Pyrolysis reactor

Fig. 1 shows the schematic diagram of the sewage sludge pyrolysis reactor. The reactor was 7 cm in diameter 40 cm

Fig. 1 also shows the experimental set-up used to collect the pyrolysis oils. The volatiles derived from the sample passed through an ice-cooled condenser and then through two icecooled U tubes with raschig rings. However, most of the oil was recovered from the rst condenser. The reactor, the condenser and the U tubes were weighed before and after the experiment. The char and pyrolysis liquid yields were calculated by measuring the gain in weight of the reactor, the condenser and the U tubes, while the gas fraction was evaluated by difference. In order to separate the aqueous and the organic fractions, dichloromethane was added. The aqueous fraction recovered in the tubes was then separated from the organic fraction by decantation and weighed. The organic fraction yield was calculated by difference. An oil solution of known concentration was prepared and analysed by GCMS. For the analysis a Hewlett-Packard HP 6890 gas chromatograph coupled to an HP 5973 quadrupole detector was used. The gas chromatograph was tted with a 60 m 0.25 mm capillary column coated with a 0.25-mm thick lm of 5% phenyl methylpolysiloxane (HP-5). Helium was employed as a carrier gas at a constant ow of 0.9 mL min1. The initial oven temperature of 40  C was held for 5 min and then

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Oven

Sewage sludge Quartz reactor He Main Condenser

Ice Oils

Ice

Gas sampling

U-Tubes with Raschig rings

Fig. 1 Schematic diagram of the sewage sludge pyrolysis reactor.

programmed from 40 to 300  C at 5  C min1 with an isotherm held for 30 min. The split ratio was 20:1 and the injection was carried out at 300  C. The ion source and transfer line temperatures were 230 and 325  C, respectively. Data were collected in the full-scan mode with mass to charge (m/z) ratios from 25 to 533 and a solvent delay of 6 min was used. The chromatographic peaks were identied with the help of the NIST mass spectral data library. In addition, identication was also carried out on the basis of the fragmentation observed and taking into account the retention times of the peaks using standard compounds when available. The changes in oil composition relating to the pyrolysis temperature were monitored by calculating the normalized area (AN) for the compounds identied in the oil. These values were obtained by dividing the peak area values by the concentration of the pyrolysis oil sample used in the chromatographic analysis. The yields of the individual compounds were calculated using a calibration curve obtained from the analysis of standard solutions with different concentrations containing the 50 compounds quantied in this study.

Table 2 also shows the results of the aqueous fraction content. For all temperatures, the water yield was higher than the moisture content of the initial sludge (6.8 wt.%). The gas yield remained fairly constant as the pyrolysis temperature increased from 350 to 550  C. However, above this temperature a signicant increase in gas yield was observed.

3.3.

GCMS characterization of the pyrolysis oils

3.
3.1.

Results
Main characteristics of the raw sewage sludge

The results of the proximate and ultimate analysis, the H/C ratio and the caloric value of the raw sewage sludge are provided in Table 1. The results show a high concentration of organic oxygen (25.8%) and a high value for the H/C atomic ratio (1.7). The gross caloric value (GCV) of the sewage sludge was 16.4 MJ kg1.

Fig. 2 shows the GCMS chromatograms of the oils obtained from the pyrolysis of sewage sludge at 350, 450, 550 and 950  C. The constituents identied in the oils in relation to pyrolysis temperature are shown in Table 3. The chromatographied fraction of all the oils obtained ranges from 2-methylpropanenitrile (peak 1, Mw 69) to n-C31 (peak 103, Mw 436). Pyrolysis oils are complex mixtures, made up of hundreds of organic compounds from a wide variety of chemical groups. The compounds identied in the oils can be grouped into the following classes of compounds: n-alkanes and 1-alkenes with a number of carbons ranging between C11 and C31; monoaromatic hydrocarbons which include benzene, toluene, styrene, phenol, 1H-indene and their alkyl derivatives; aromatic compounds containing nitrogen and oxygen such as pyridine, alkyl pyridines, 1H-pyrrole, 1H-indole, isoquinoline, methylquinolines, 9H-carbazole and benzofurane; aliphatic and aromatic nitriles; carboxylic acids (RCOOH), where R represents long aliphatic chains with 14, 15, 16 and 18 carbon atoms; long chain aliphatic amides and steroids such as cholestene, cholestadiene or formyl cholestene. Polycyclic aromatic hydrocarbons (PAHs) including naphthalene, methylnaphthalenes, biphenyl, acenaphthylene, uorene, phenanthrene, anthracene, benzo[g]quinoline, methylphenanthrenes, 11H-

3.2.

Product yields
Table 2 Product yields (wt.%) from the pyrolysis of sewage sludge. Final pyrolysis temperature ( C)
Char Oil Water Gases

The oil, char, gases and aqueous fraction yields in relation to the process conditions in the reactor are shown in Table 2. The char yield decreased with a rise in pyrolysis temperature from 52% at 350  C to 39% at 950  C. The oil yield reached a maximum value at 450  C with a value of 13 wt.% and it decreased with increasing temperature to 9% at 550  C. Above this temperature the oil yield remained constant.

350
52 10 18 20

450
47 13 18 22

550
49 9 21 21

950
39 9 20 32

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biomass and bioenergy 33 (2009) 933940

41 93 28 22 37 47 57 5
. . .

72
350 C

79

32 62.. 85 15 . 6 . 51 . . . . 26 .. . .. . . .. . 4 7 . . 20 . .. . . 102 . .. .. . . . .. . ... . . ... . . .. .. . . .. . ... . . . .. . . . .. . . . . .

450 C

550 C

950 C

10

15

20

25

30

35

40

45

50

55

60

65

70

75

Time (min)
Fig. 2 GCMS chromatograms of the oils obtained from the pyrolysis of sewage sludge at increasing temperatures.

benzo[a]uorene, benzo[a]anthracene, chrysene and benzo[a]pyrene were also detected in these oils. The evolution of the oil composition with the pyrolysis temperature was evaluated by the variation in the normalized areas values (AN) for the identied compounds, which are given in Table 3. Obviously, the data presented in the table are not absolute and can only be used to indicate trends. Table 4 shows the concentration of the main compounds present in the pyrolysis oils. The major compounds are carboxylic acids, phenol, p-cresol and 1H-indole. The maximum values are observed at 350  C e.g. hexadecanoic acid (17.71 wt.%), tetradecanoic acid (4.77 wt.%), 9-

octadecanoic acid (4.73 wt.%), phenol (2.40 wt.%), p-cresol (2.46 wt.%) and 1H-indole (1.58 wt.%). The concentration of some mono-aromatic hydrocarbons also showed signicant values. For example, benzene, toluene, total xylenes, styrene and indene increase from 1001 to 4482 ppm, 452011,940 ppm, 20183703 ppm, 30365312 ppm and 40036784 respectively, as the temperature increases from 350 to 950  C. Pyridine and 1H-pyrrole reach values of up to 7290 and 9063 ppm, respectively at 950  C. The total amount of identied aliphatic hydrocarbons decreased from 1.43 wt.% at 350  C to 0.96 wt.% at 950  C. Signicant quantities of PAHs were also found, even at the lowest temperature of 350  C.

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937

Table 3 Evolution of the normalized area (AN)a with pyrolysis temperature. Pk no

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61

Table 3 (continued ) Pk no
62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103

Compound
2-Methylpropanenitrile Benzene 3-Methylbutanenitrile Pyridine 1H-Pyrrole Toluene 2-Methylpyridine 2-Methylpyrazine 4-Methylpentanenitrile 2-Methyl-1H-pyrrole Furfuryl alcohol 3-ethylpyrydine Ethylbenzene 1,4-dimethylbenzene Styrene 1.2-dimethylbenzene Dmethylpyrazine 2-Ethylpyridine 2,5-dimethyl-1H-pyrrole 2,4-dimethylpyridine 3-ethylpyridine Phenol Benzonitrile Methylstyrene Benzofurane 1H-Indene o-Cresol p-Cresol 1-Undecene 4-Methylbenzonitrile 3-methylbenzonitrile Benzeneacetonitrile 2,4-dimethylphenol Methylindene p-Ethylphenol 1-Dodecene Naphthalene Benzenepropanenitrile Isoquinoline 1-Tridecene 1H-Indole 2-Methylnaphthalene 1-Methylnaphthalene Methylquinoline 1-Tetradecene Biphenyl 4-Methyl-1H-Indole Dimethylnaphthalene Dimethylnaphthalene 2-Ethenylnaphthalene Acenaphthylene 1-Pentadecene n-Pentadecane 2,3-Dimethylindole Naphthalencarbonitrile Naphthalencarbonitrile 1-Hexadecene n-Hexadecane 9H-Fluorene 1-Heptadecene n-Heptadecane

RTb

Compound
Tetradecanoic acid 1-Octadecene Phenanthrene Anthracene Pentadecanoic acid Methyltetradecanoic acid Benzo[g]quinoleine 9H-Carbazole Hexadecanenitrile Methylphenanthrene Methylphenanthrene Hexadecanoic acid 2-Phenylnaphthalene Tetradecenamide Tetradecanamide Fluoranthene 9-Octadecenoic acid Pyrene Hexadecanamide n-Docosano 11H-Benzo[a]uorene n-Tricosane Octadecenamide Octadecenamide n-Tetracosane n-Pentacosane Benzo[a]anthracene Chrysene Di-(2-ethylhexyl)phthalate n-Hexacosane n-Hepatacosane n-Octacosane 3-Cholestene 5-Cholestene Cholestene n-Nonacosane Cholestene Cholestene Benzo[a]pyrene Cholestadiene n-Triacontane Formyl cholestane n-C31

RTb
40.89 41.47 42.01 42.22 42.40

AN 350c

AN 450c

AN AN 550c 950c

AN 350c
4866 1652 3230 4548 3477

AN 450c
4391 1320 6999 5301 3171

AN AN 550c 950c
1619 855 3462 2899 1530 957 1153 885 528 1171 6802 1307 826 573 1922 1273 2589 2218 471 887 343 800 1063 1321 659 925 1715 230 718 566 399 4958 2970 360 260 1244 502 922 994 0 1350 740 1871 895 5766 4137 1991 1445 1797 1519 544 1312 9396 980 1343 1051 3867 2502 4589 3270 758 1225 584 835 818 1835 1067 1436 2305 354 1403 1118 869 5337 3643 607 649 1514 724 1728 1183 307 1561 748

6.98 544 0 271 368 7.89 288 527 779 1290 10.01 1112 504 738 759 10.50 2820 2292 3704 4176 10.97 4398 3150 4789 4460 11.37 2911 4440 7299 7690 13.22 2942 2237 3087 2970 13.49 1003 713 852 861 14.26 1861 980 1332 1356 14.56 1142 753 1001 1200 14.86 1352 0 0 0 15.01 1619 1376 1405 1518 15.06 2551 2490 3343 3407 15.36 1235 1508 2737 2480 16.21 3152 3523 6221 5513 16.30 888 914 1601 1416 16.41 520 0 468 477 16.69 390 0 488 467 17.48 1295 753 905 1053 17.64 3086 1891 2256 2207 18.71 862 0 532 575 19.62 15,402 11,679 7010 7794 19.77 4250 4296 3422 3472 20.07 1138 1156 1881 1755 20.21 857 1121 1701 1881 21.93 2791 2516 3649 4729 22.15 3274 2461 1716 1768 22.87 19,459 13,884 13,937 16,657 23.22 1963 1637 1982 1712 23.42 3745 2891 2003 1485 23.90 1616 3346 1956 2634 25.01 4669 2864 2225 2256 25.26 4831 5041 2644 3582 25.39 3745 2061 1974 2058 25.84 4683 4233 1688 2657 26.36 1176 1493 2428 2637 26.58 8575 9718 8733 7778 28.12 2108 1548 687 1128 28.21 3991 4693 1679 2625 29.28 2172 1400 870 816 29.79 15,704 13,502 10,231 10,888 29.84 4511 5055 3163 4194 30.35 3003 3226 2161 1834 31.46 1468 1941 678 832 32.01 3116 1757 1794 1109 32.12 1098 5256 1146 1265 32.32 8129 9592 3455 4141 33.27 1878 1885 1164 1203 33.36 884 911 627 614 33.50 1293 1399 790 898 34.15 3162 5460 2253 4304 34.58 2531 3009 1973 2435 34.76 1901 1278 986 1092 35.02 818 1546 928 866 35.27 1163 1999 802 1420 35.91 1501 1451 1316 1744 37.00 3662 3175 1849 2094 37.16 949 960 707 803 37.44 1325 2308 1069 1779 39.29 1550 1135 569 628 39.45 986 872 470 592 (continued on next page)

42.95 1276 1356 43.10 2558 2518 43.81 1644 1600 44.36 650 827 44.50 1632 1999 45.04 18,064 16,012 45.82 1228 1748 46.55 1601 1534 46.73 1161 1081 47.73 1922 3078 48.44 4821 4093 48.77 3864 4378 49.16 4471 4244 49.28 980 733 50.44 1046 1763 51.00 829 585 52.26 1578 1337 52.34 2554 2211 52.63 2664 2323 54.22 1762 1090 54.52 734 1395 54.71 974 2854 55.19 578 534 55.74 1889 1114 57.22 1912 968 58.74 1492 634 59.51 8410 7589 59.96 5326 4741 60.34 885 726 60.43 1034 0 60.51 2377 2065 60.68 939 823 61.28 760 1573 61.46 1873 1715 62.33 973 0 63.23 2510 2191 64.56 1183 921

a AN: normalized area obtained dividing the peak area values by the concentration of the pyrolysis oil sample (ppm). b RT: retention time (min). c AN 350, AN 450, AN 550 and AN 950: normalized area for the compounds identied in the pyrolysis oils obtained at 350, 450, 550 and 950  C, respectively.

4.
4.1.

Discussion
Main characteristics of the raw sewage sludge

The values in Table 1 reect the presence of a large number of functional groups and the strongly aliphatic nature of the sludge. The gross caloric value (GCV) of the sewage sludge was similar to the lower limit of other wastes such as plastics, wood, paper, rags and rubbish, presenting a GCV in the range

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Table 4 Concentration (ppm) of the main compounds present in the pyrolysis oils. Pk no Compound RT (min) 350
2 4 5 6 14 15 16 18 21 22 23 26 27 28 29 36 37 39 40 41 42 43 45 51 52 53 57 58 59 60 61 62 63 64 72 76 77 78 80 82 85 86 87 88 90 91 92 99 101 103 Benzene Pyridine 1H-Pyrrole Toluene 1,4-dimethylbenzene Styrene 1,2-dimethylbenzene 2-Ethylpyridine 3-ethylpyridine Phenol Benzonitrile 1H-Indene o-Cresol p-Cresol 1-Undecene 1-Dodecene Naphthalene Isoquinoline 1-Tridecene 1H-Indole 2-Methylnaphthalene 1-Methylnaphthalene 1-Tetradecene Acenaphthylene 1-Pentadecene n-Pentadecane 1-Hexadecene n-Hexadecane 9H-Fluorene 1-Heptadecene n-Heptadecane Tetradecanoic acid 1-Octadecene Phenanthrene Hexadecanoic acid Fluoranthene 9-Octadecenoic acid Pyrene n-Docosane n-Tricosane n-Tetracosane n-Pentacosane Benzo[a]anthracene Chrysene n-Hexacosane n-Heptacosane n-Octacosane Benzo[a]pyrene n-Triacontane n-Untriacontane

Final pyrolysis temperature ( C) 450 550 950

4482 7290 9063 11,940 2357 5312 1346 516 636 12,140 3591 6784 2232 21,022 875 1347 4881 2422 417 10,931 2576 1126 567 2267 1066 478 916 351 814 275 259 18,348 390 2675 92,125 1814 24,528 1899 234 180 566 329 408 654 429 341 265 586 94 228

7.89 1001 1833 2706 10.50 4924 4001 6467 10.97 8936 6401 9731 11.37 4520 6893 11,333 15.36 1174 1433 2601 16.21 3036 3394 5994 16.30 844 869 1522 16.69 431 539 18.71 953 588 19.62 23,990 18,190 10,919 19.77 4396 4443 3539 21.93 4003 3608 5235 22.15 4132 3105 2165 22.87 24,558 17,523 17,589 23.22 1003 837 1012 26.36 601 762 1240 26.58 5382 6099 5481 28.21 3683 4331 1550 29.28 1110 715 445 29.79 15,766 13,556 10,271 29.84 2771 3105 1943 30.35 1845 1981 1328 32.01 1592 897 917 34.15 1666 2877 1187 34.58 1108 1317 864 34.76 832 559 431 37.00 1603 1389 809 37.16 415 420 310 37.44 607 1056 489 39.29 679 497 249 39.45 431 382 206 40.89 47,708 43,054 15,873 41.47 719 575 372 42.01 1499 3248 1607 45.04 17,7104 156,988 66,686 47.73 901 1444 902 48.44 47,265 40,126 12,483 48.77 1599 1812 1071 49.28 302 226 145 51.00 256 180 106 52.63 821 716 407 54.22 543 336 203 54.52 208 396 263 54.71 276 810 487 55.74 577 340 219 57.22 584 296 173 58.74 456 194 122 61.28 258 533 313 62.33 297 64.56 361 281 226

The decrease in the char yield as the pyrolysis temperature increased is to be attributed to an increasing de-volatilization of the solid hydrocarbons in the char, although partial gasication of the carbonaceous residue is also possible [24]. Other researchers using ash pyrolysis [19] and a uidized bed reactor [20] also observed signicant decreases in char yield as the pyrolysis temperature of sewage sludge increased. For all temperatures, the water yield was higher than the moisture content of the initial sludge (6.8 wt.%) indicating that water was formed during pyrolysis. This can be explained by the breaking up of functional groups from the volatile compounds during homogeneous secondary reactions. The increase in gaseous products was due to the secondary cracking of the pyrolysis vapours at higher temperature. Nevertheless, as already mentioned, the secondary decomposition of the char at high temperatures may also give noncondensable gaseous products, owing to a heterogeneous reaction between the char and gaseous components such as H2O [24]. From the results in Table 2, the production of gas seems to be predominantly due to the decomposition of char rather than the oil since there was a greater decrease in char yield when the pyrolysis temperature was increased. The oil and char yields obtained were lower and higher respectively, than those obtained by other researchers [19]. These differences are due to the conditions used in this paper: slow pyrolysis and long hot-zone residence times for the volatile products. At low temperatures, these parameters are known to increase the yield of char at the expense of oil formation. At higher temperatures, gas formation is favoured, although char continues to be the main product.

4.3.

GCMS characterization of the pyrolysis oils

17.620.0 MJ kg1, while coal has a GCV between 14.6 and 26.7 MJ kg1 [23].

4.2.

Product yields

Under the experimental conditions established in this work, the results showed a clear inuence of temperature on the fraction yields.

Although the qualitative composition of the oils is the same, the different proles of the chromatograms (Fig. 2) indicate that the pyrolysis temperature had a profound effect on the composition of the oils. Table 3 shows that the concentrations of long chain nalkanes and 1-alkenes diminished with increasing pyrolysis temperature. Lighter 1-alkenes ranging from 1C11 to 1C14 were observed in the oil while the corresponding n-alkanes were absent at any temperature. For the medium aliphatic hydrocarbons (from C15 to C17) both 1-alkene and n-alkane were identied, the decrease in concentration with the temperature being higher for the 1-alkene than for the corresponding nalkane. Finally, it should be pointed out that only n-alkanes with a carbon atom number higher than 22 were detected. As the temperature of pyrolysis is increased from 350 to 950  C, the mono-aromatic hydrocarbon concentration in the oils grew. Styrene and xylenes reached a maximum concentration at 550  C and above this temperature the concentration decreased slightly. In a work on tyre pyrolysis [15] using a static bed reactor, the concentration of mono-aromatic hydrocarbons increased as the pyrolysis temperature rose to 525560  C. However at 600  C there was a fall in concentration. Unlike the mono-aromatics, phenol and its alkyl derivatives showed a strong decrease in their concentrations as pyrolysis temperature rose. Other authors [17] observed that in oils from the ash pyrolysis of biomass the formation of

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phenol and its alkylated derivatives tended to increase as the pyrolysis temperature increased up to 550  C. As regards aromatic nitrogenated compounds, pyridine and 1H-pyrrole exhibited an increase in their concentrations with temperature, whereas the concentration of isoquinoline, methylisoquinoline, 9H-carbazole and 1H-indole, all of which are polyaromatic compounds, showed a decrease as pyrolysis temperature rose. Within the nitrile group, aliphatic and mono- and poly-aromatic compounds such as benzonitrile or naphthalen carbonitrile were found. In all cases a clear decrease with temperature was observed. It should be noted that benzofurane, the oxygen-containing compound analogous to 1H-indole, underwent a substantial growth in concentration with rising temperatures. This increase was even higher than that of the corresponding hydrocarbon 1H-indene. A similar behaviour was also observed by other authors for benzofurane [17]. The corresponding data for the long chain aliphatic carboxylic acids reported in Table 3 clearly showed a decrease with temperature. The predominant step in the cracking reactions of these compounds is de-carboxylation which gives rise to CO2 and hydrocarbon radicals, the latter undergoing disproportionation, isomeration and hydrogen transfer to produce hydrocarbons. Amides and steroids exhibited the same trend as the carboxylic acids: there was a decrease in their concentration as the pyrolysis temperature increased. Another important constituent of pyrolysis oils from an environmental point of view is polycyclic aromatic hydrocarbons (PAHs) since some of these compounds have been shown to be carcinogenic and/or mutagenic. Changes in these indicated that PAHs with 23 rings like naphthalene, alkylnaphthalenes, biphenyl, acenaphthylene, 9H-uorene, phenanthrene, alkylphenanthrenes and 2-phenylnaphthalene passed through a maximum at a pyrolysis temperature of 450  C. This tendency was not clear for PAHs with 45 rings. Most of these hydrocarbons also showed a considerable increase with temperature up to 450  C, their concentration at 950  C being slightly higher than at 450  C. After examining different pyrolysed waste materials, Williams et al. (1994) found that as the temperature of pyrolysis increased up to 720  C, the concentration of the PAHs in the oils also increased. However, McGrath et al. (2003) observed that the formation of PAH from the pyrolysis of cellulose reached a maximum at a pyrolysis temperature of 500600  C. With regard to structure, PAHs with an alkyl or methylene group (CH2) showed a greater decrease than the corresponding PAH. For example, alkyl napththalenes showed a greater reaction to temperature than naphthalene, whereas the reactivity of 9H-uorene and 11H-benzo[a]uorine was higher than that of phenanthrene and uoranthene, respectively. The formation of PAHs can be explained by several reaction pathways. A DielsAlder reaction mechanism has been suggested by several authors [15,16] as responsible for the formation of these compounds. It is assumed that the pyrolysis of alkanes at high temperatures gives rise, via dehydrogenation to alkenes and dienes which by cyclization and subsequent aromatization produce the aromatic compound [25,26]. In the present work, the decrease in aliphatic compounds with the pyrolysis temperature

suggested that PAHs were formed via a DielsAlder mechanism. The growth of aromatics into higher molecular compounds might also occur via a DielsAlder reaction. However, other routes of formation for PAHs have also been suggested e.g. direct combination of aromatic rings and/or H2 abstraction C2H2 addition [27]. Previous studies [25,28] of pure compounds have also provided evidence that secondary reactions of oxygenated compounds such as phenols, cresols and xylenols at moderate to high temperatures can produce mono-aromatics and PAHs via deoxygenation. This mechanism would be in accord with the results in Table 3 which indicate that there was a loss of phenol, o- and p-cresol, 2,4dimethylphenol and p-ethylphenol and an increase in mono and polyaromatic hydrocarbons as the severity of pyrolysis increases. The long residence times used in this work would favour the formation of PAHs by increasing the number of possible secondary reactions between the volatile products (Table 4). P The PAHs was 1.70, 2.34, 1.51 and 1.97 wt.% at 350, 450, 550 and 950  C, respectively. From the point of view of concentration the most important PAH, at any pyrolysis temperature, was naphthalene (6099 ppm at 450  C). The 23 rings PAH maximum yields, were 5086, 2877, 1056 and 3248 ppm, corresponding to alkylnaphthalenes, acenaphthylene, uorene and phenanthrene, respectively, at 450  C. Of the largest PAHs, uoranthene and pyrene show the highest concentrations with values of 1814 and 1899 ppm respectively, at 950  C. Nevertheless, benzo[a]anthracene, chrysene and benzo[a]pyrene, which were detected at a temperature as low as 350  C, also show high values taking into account their high level of toxicity.

5.

Conclusions

In this work it has been shown that sewage sludge pyrolysis oils contain signicant quantities of potentially high value hydrocarbons such as mono-aromatic hydrocarbons and phenolic compounds. The concentrations of phenol and pcresol, in particular, reached in both cases a maximum concentration of 2.4 wt.% in the oil obtained at the low temperature of 350  C. However, the main oil component was hexadecanoic acid (up to 17.7 wt.% at 350  C). Monitoring of the compounds during the pyrolysis of sewage sludge with increasing temperatures was carried out by means of GCMS. It was demonstrated that, as the temperature of pyrolysis increased from 350 to 950  C, the concentration of monoaromatic hydrocarbons in the oils also increased. Conversely, phenol and its alkyl derivatives showed a large decrease in their concentration with temperature. The oils were also found to contain substantial concentrations of PAHs, even at the low temperature of 350  C. The evolution of these compounds indicates that PAHs with 23 rings passed through a maximum at a pyrolysis temperature of 450  C. PAHs with 4 5 rings also presented a substantial increase with temperature up to 450  C, their concentrations at 950  C being slightly higher than that at 450  C. The pathway to PAH formation is believed to be via a DielsAlder reaction and also via secondary reactions of oxygenated compounds such as phenols.

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Acknowledgements
The authors thank the Spanish Ministry of Science and Technology (Research Project PPQ2001-2083-C02-01) and FEDER for nancial support. A. Domnguez is also grateful to FICYT (AsturiasSpain) for nancial assistance.
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