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Technical note
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Article history: In the present study, ten different types of dewatered sewage sludges were treated in supercritical water
Received 11 April 2013 in a high-pressure autoclave under a given condition (at 400 C, 60 min and 23 MPa). The feasibility of
Accepted 13 January 2014 direct gasication and the effect of sludge properties on the gasication of dewatered sewage sludge
Available online 4 February 2014
with various properties in supercritical water were investigated. The results showed that dewatered
sewage sludge with various water contents (73.48e88.51 wt%), organic matter contents (29.25e73.02 wt
Keywords:
%, on dry basis) and inorganics can be directly gasied in supercritical water. The total gas and phenol
Sludge property
production increased linearly with the increment of organic matter content in dewatered sewage sludge.
Supercritical water gasication
Sewage sludge
The difference in hydrogen content in the gaseous product may be related to the content of water and
Phenol inorganic as well as pH value of the sludge. The char/coke formed in the solid residue increased with
Char/coke decrement of water content, which inhibited the gasication reaction and resulted in the carbonization
reaction.
2014 Elsevier Ltd. All rights reserved.
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http://dx.doi.org/10.1016/j.renene.2014.01.006
606 M. Gong et al. / Renewable Energy 66 (2014) 605e611
2.1. Materials The method used for analysis of gas, liquid, solid residue and the
procedures for char separation and preparation were described in
In this work, ten different types of DSSs (named S0 to S9) were detail in Ref. [16]. The sludge samples were air-dried, pulverized
collected from WWTPs in Jiangsu, China. The locations of the and then sieved under a 100-mesh before analysis. The elemental
WWTPs and the types of industrial wastewater are shown in Fig. 1. compositions (C, H, N, and S) of the sludge samples were measured
DSS was collected from the WWTPs and stored in the preservation by an elemental analyzer (Vario EL III, Elementar). The inorganic
box of a refrigerator at a temperature below 4 C before experiment. elements (Na, K, Ca, Mg, Fe and Ni) in the sludge samples were
The compositions, in terms of the content of OM, moisture, and ash, determined by ICPeOES (Optima 8000, PerkinElmer). The pH value
as well as ultimate analyses of each type of DSS, are listed in Table 1. of the liquid and raw sludge was measured by a pH meter (FE20,
The inorganic element composition of each type of DSS is listed in Mettler Toledo). Besides, the parameter RLiquid is the ratio of OM
Table 2. residues in liquid, as dened in Ref. [16].
The SCWG of DSS was performed in a 316 L stainless steel batch 3.1. The state of the product after the SCWG
reactor obtained from the Songling Chemical Instrument Co., Yan-
tai, Shandong, China. The schematic presentation of the reactor is The DSS (S0eS9) used in this study had water contents in the
shown in Fig. 2. The reactor has a 100-mL capacity and a maximum range of 73.48e88.51 wt%, based on the water content demanded to
operating temperature and pressure of 650 C and 35 MPa, attain supercritical conditions at 400 C (i.e., 33 mL), we calculated
M. Gong et al. / Renewable Energy 66 (2014) 605e611 607
Table 1
Properties of the dewatered sewage sludges tested.
Type of sludge Organic matter Moisture content Ash (wt.%)a pHb Ultimate analysis (wt.%)a HHV (MJ/kg)d Sewage
(wt.%)a (wt.%) treatment processe
C H N S Oc
S0 29.25 77.91 54.49 8.06 7.60 2.53 0.37 0.91 34.09 0.17 AS
S1 30.94 73.48 57.78 7.97 16.25 2.29 0.62 2.85 20.22 5.44 A/O
S2 37.40 74.79 54.05 6.80 9.14 3.94 1.38 1.03 30.47 3.41 OD
S3 46.05 88.51 48.71 5.92 18.02 4.06 2.79 1.95 24.47 7.78 A/A/O
S4 49.57 84.73 49.03 7.57 17.14 3.96 2.93 1.16 25.78 7.03 UASB
S5 51.09 86.91 48.18 6.59 20.39 4.15 3.05 1.30 22.93 8.94 A/A/O
S6 54.44 85.41 44.91 6.97 22.08 4.41 3.53 1.05 24.02 9.67 CAST
S7 59.52 86.29 41.19 6.40 25.05 4.70 3.84 1.21 24.02 11.11 OD
S8 63.94 87.75 38.20 6.91 27.56 5.20 1.58 2.49 24.97 12.60 CAST
S9 73.02 73.99 24.33 3.71 31.00 6.20 1.22 3.34 33.91 13.68 A/O
a
On an air-dried basis.
b
The ratio of water to solid was 20.
c
By difference (O% 100% ash% C% H% N% S%).
d
Higher heating value (HHV) calculated by the Dulong Formula, i.e., HHV (MJ/kg) 0.3393C 1.443 (H O/8) 0.0927S 0.01494N.
e
AS: activated sludge process; A/O: aerobic-oxic; OD: oxidation ditch; A/A/O: anaerobic-anoxic-oxic; UASB: up-ow anaerobic sludge bed; CAST: cyclic activated sludge
technology.
the amount of the DSS fed is listed in Table 3. The indicated pressure after SCWG at 400 C for 60 min. The liquid residues contained
in the autoclave when the temperature was reached and stabilized at large amounts of OM. COD in the liquid residues ranged from about
the pre-set points of the reactor is also listed in Table 3. The pressures 3500 to 17,000 mg/L. The ratios of OM in the liquid residues (RLiquid)
in the reactor ranged from 22.5 to 24 MPa, and averaged at 23.4 MPa, ranged from 3.3% to 18.0%. The remaining OM in the liquid residues
which were higher than the critical pressure (22.1 MPa) of the water, exceeded wastewater discharge standards and required further
indicating that the water was in a supercritical state in all cases. The removing.
state of the products in the reactor indicated that gaseliquidesolid Phenol, as a representative pollutant, needs to be taken into
three-phase separation was obtained, regardless of the source of the consideration in the processing and utilization of the liquid prod-
DSS. The mass components of the products are listed in Table 3. The ucts after SCWG treatment [6,16]. The concentrations of total
amount of solid residue that adhered to the reactor inner wall after phenols in the liquid products of different DSSs after SCWG are
SCWG of the DSS increased with decreasing water content. This led shown in Fig. 5. The contents of phenolic substances produced in
to obvious differences in the products of the total mass and the feed each sample varied greatly, from approximately 400 mg/L in S9 to
amounts (S1, S9). 50e200 mg/L in the other sludges.
Table 2
Inorganic element compositions of the dewatered sewage sludges tested.
Na K Ca Mg Fe Ni
Table 3
The recovery rate of the product and the reaction pressure after SCWG.
Type of sludge S0 S1 S2 S3 S4 S5 S6 S7 S8 S9
Dewatered sludge (g) 42.3 44.8 44.0 37.2 38.9 37.9 38.5 38.1 37.5 44.5
Total product mass (g) 34.4 32.4 42.3 32.3 34.3 33.4 34.0 33.5 34.2 33.2
Recovery ratea (%) 81.32 72.32 96.12 86.69 88.09 88.06 88.30 87.82 91.32 74.64
Dry sludge (g) 9.3 11.9 11.1 4.3 5.9 5.0 5.6 5.2 4.6 11.6
Organic matter mass (g) 2.7 3.7 4.1 2.0 2.9 2.5 3.1 3.1 2.9 8.5
Reaction temperature 400 C
Reaction pressure (MPa) 23.3 23.2 24.0 23.8 23.3 22.5 23.8 23.0 23.6 24.1
a
Recovery rate Total product mass/dewatered sludge 100%.
48.1%, depending on the change in the OM content of the original conclude that the water in the DSS has reached the supercritical
sludge. state. Xu et al. [16] experimented with one type of DSS at different
To reveal the effects of DSS properties on the carbonization re- moisture contents (76.2e94.4 wt%) and found that the water in all
action, the char/coke content in the solid phase products after the samples was able to enter the supercritical state normally. DSSs
reaction was measured, and the total char/coke mass was calcu- with various properties after the gasication reaction are in the
lated. The results are shown in Fig. 7. The char/coke contents in the same state, in which the gas, liquid and solid phases are apparently
solid phase products ranged from 5.7% to 47.4%, and the char/coke separated. These results are consistent with results obtained by
masses ranged from 0.2 g to 2.3 g. other scholars in researchs on SCWG of sludge [18,19]. In addition,
the OM in the DSS after reaction can successfully be transformed
3.5. The OM distribution of gasication products into liquid and gaseous products, and the components of the gas
products and the forms of the liquid- and solid-phase organics are
From the OM residues in the gasication products after SCWG, all similar (Fig. 8). Thus, we can conclude that the components of
we determined the distributions of OM in three-phase products the products after gasication of DSSs with various properties in
shown in Fig. 8. The OM in the DSS remained in three-phase SCW are similar and exhibit no fundamental differences.
products after SCWG. DSSs with different properties can go
through the SCWG reaction normally. However, the conversion
efciency of organics is not high with approximately 30% of OM
remaining in the liquid and solid products.
4. Discussion
Fig. 3. Effects of DSS properties on the gas yield and the yields of primary gaseous
products. Fig. 5. Total phenols concentration of different DSSs after SCWG at 400 C for 60 min.
M. Gong et al. / Renewable Energy 66 (2014) 605e611 609
Fig. 6. The OM content changed in the solid phase of different DSSs before and after
SCWG at 400 C for 60 min.
Fig. 8. The OM distribution in gasication products of the DSSs.
Fig. 7. The contents and mass of char/coke in solid residue of different DSSs after
SCWG at 400 C for 60 min. Fig. 9. Effects of OM content on gas yield from the SCWG of DSS.
610 M. Gong et al. / Renewable Energy 66 (2014) 605e611
decreasing water content. This also means that when the water
content of the DSS decreases, the gasication reaction is inhibited.
Meanwhile, the carbonization reaction is promoted and the trans-
formation of OM into char/coke is increased. This is consistent with
the results of previous studys analysis of the char/coke content of
the product after the reaction of DSS with different moisture con-
tents [16]. We noted that char/coke is mainly generated from
devolatilization of the original biomass when the moisture content
is low. Xu et al. [14] obtained the same results from SCWG of SPP at
a reaction temperature of 280 C. An increase in the dry matter
content of sludge from 4.8 wt% to 16.7 wt% (with the water content
ranging from 95.2 wt% to 83.3 wt%) resulted in an increased yield of
char/coke content in the solid phase residues. Thus, there is a ne-
cessity to inhibit the carbonization reaction occurring and improve
the efciency of organics gasication in the future research.
From the perspective of technology popularization and appli-
cation, SCWG technology was found to have common effects on
DSSs with various properties. We did not need to adjust the
Fig. 10. Effects of OM content on total phenol production from the SCWG of DSS. apparatus for the different types of sludge, which was benecial to
the design of the treatment. However, issues such as the feed of
water contents of S3, S7 and S8 were relatively high (Table 1). sludges with low water contents and reactor clogging and corrosion
Zhang et al. [6] noted that increasing the water content can improve need to be considered [1e3]. Differences in the results obtained
the generation of hydrogen and methane. As shown in Fig. 10, the using different types of reactor should also be considered. A ow-
OM content of DSS exhibits an obvious increasing trend in the type reactor may be used to improve treatment efciency in prac-
quantity of phenols formed (except for the large deviations for S3). tical applications. Besides, the cost accounting, resource utilization
Zhang et al. [6] obtained similar results: the higher the OM content and energy balance of the products also need to be considered. In
in SPP, the higher the content of heavy oil (mainly phenols) in the addition, the controls on the use of SCWG technology to treat
products. Some studies have noted that the phenolic compounds hazardous waste such as sludge should be more rigorous and
originate primarily from the degradation of the lignin component detailed to ensure the environmental safety of the products.
(due to cleavage of the aryl ether linkages in lignin) [29,30]. In
addition, condensation/cyclization of the cellulose/hemicellulose- 5. Conclusions
derived carbohydrates might also lead to the formation of phenol
and phenolic compounds [31]. The composition of organics in the A comprehensive study of SCWG of DSS with various properties
sludge is complex, consisting mainly of carbohydrates, cellulose, was performed. The effect of DSS properties on the SCWG of DSS
hemicellulose, lignin, protein, fat and other substances [32]. The was investigated in this study. The gas yields and compositions, OM
OM in sludge may go through decomposition and condensation to content in liquid and solid, and total phenols and char/coke content
form phenols in SCW. The subsequent processing of the liquid were measured to determine the effects of the DSS properties. The
product after reaction needs to be conducted taking into consid- major conclusions of the present study can be summarized as
eration how to reduce the generation of phenols. Adding an follows:
oxidizing agent to achieve partial oxidation gasication is an
effective way to solve this problem [33]. (1) DSSs with various water contents (73.48e88.51 wt%), OM
The effect of water content on char/coke formation during the contents (29.25e73.02 wt%) and inorganics can be directly
SCWG of DSSs with various properties was investigated. The results gasied in supercritical water. However, the conversion ef-
are illustrated in Fig. 11. Char/coke formation increased with ciency of organics is not high with approximately 30% of
OM remained in the liquid and solid residues.
(2) The total gas and phenol production increased linearly with
the increasing of OM content in DSS.
(3) Differences in hydrogen content in the gaseous product may
be related to differences in the inorganic compounds, water
content and pH value of the DSS samples.
(4) Carbonization occurred during the SCWG of the DSS. The
char/coke formed in the solid residue increased with decre-
ment of water content, which inhibited the gasication re-
action and resulted in the carbonization reaction. Therefore,
methods to inhibit the carbonization or improve the gasi-
cation efciency during the direct gasication of DSS should
be studied in the future.
Acknowledgments
The authors are grateful for the nancial support from the
Natural Science Foundation of Jiangsu Province (BK2011025), the
Natural Science Foundation (51278165) of PR China, and the Na-
tional Program on Key Basic Research Project of China
Fig. 11. Effects of water content on char/coke production from the SCWG of DSS. (2012CB719804).
M. Gong et al. / Renewable Energy 66 (2014) 605e611 611
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