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Energy Procedia 107 (2017) 357 362

3rd International Conference on Energy and Environment Research, ICEER 2016, 7-11 September
2016, Barcelona, Spain

Effect of Oxidation Coefficient on Products of Sewage Sludge

Treatment in Supercritical Water
Guike Lin, Donghai Xu*, Zhijiang Ma, Shuzhong Wang, Yang Guo
Key Laboratory of Thermo-Fluid Science & Engineering, Ministry of Education, School of Energy and Power Engineering, Xian Jiaotong
University, Xian, Shaanxi Province 710049, China

Abstract

Supercritical water treatment is a promising technology for sewage sludge disposal. The influences of oxidation coefficient (OC)
as well as temperature on products of sewage sludge treatment in supercritical water were studied systematically. The results
show that CO2 yield obviously increased with raising OC or temperature. Oxidant helped to convert N-containing compounds
into N2. A small amount of oxidant increased H2 yield but excess oxidant decreased it. OC had significant effect on the COD
(chemical oxygen demand) and NH3-N (ammonia nitrogen) concentration of liquid products. Most of organic compounds
disappeared at OC=1.0 as temperature changed from 450 to 500 , and diethyl phthalate was main stubborn substance in the
liquid phase. The contents of some elements (such as Si, Al and Ca) in solid residue was almost double compared with those in
dry basis SS.
2017
2016Published
The Authors. Published
by Elsevier by Elsevier
Ltd. This Ltd.
is an open access article under the CC BY-NC-ND license
Peer-review under responsibility of the scientific committee of the 3rd International Conference on Energy and Environment
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Research. under responsibility of the scientific committee of the 3rd International Conference on Energy and Environment Research.
Peer-review

Keywords: Oxidant; oxidation coefficient; sewage sludge; supercritical water

1. Introduction

Sewage sludge (SS) is one of the products of city wastewater treatment. In recent decades, SS has become a
public focus because of its environmental harm and ever-increasing amount [1,2]. SS consists of plenty of water,

* Corresponding author. Tel.: +86-29-82665749; fax: +86-29-8266-8703.

E-mail address: haidongxu93346423@aliyun.com (D.H. Xu)

1876-6102 2017 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the scientific committee of the 3rd International Conference on Energy and Environment Research.
doi:10.1016/j.egypro.2016.12.176
358 Guike Lin et al. / Energy Procedia 107 (2017) 357 362

nontoxic organic and inorganic compounds, toxic organic pollutants, heavy metals, viruses, bacteria and other
pollutants [3,4]. SS disposal is an important problem for the development of water treatment industry, due to the
high concentration of heavy metals, organic pollutants and pathogens and other microbiological pollutants [5].
Traditional land utilization, landfill and incineration, etc, are the main methods of SS disposal. However, those
ways are facing great challenges such as secondary pollution, low economy and incompletely disposal [3,6]. Using
the special properties of supercritical water (SCW), can quickly and thoroughly decompose toxic organic
compounds of MSS into non-toxic substances. SCW treatment methods contain supercritical water gasification,
supercritical water partial oxidation and supercritical water oxidation technologies with oxidants content rising [7].
Combustible gases (e.g., H2, CH4) can be generated by SS supercritical water gasification or supercritical water
partial oxidation technology by using oxidant less than theoretical oxygen demand.
In this work, the influences of oxidation coefficient on the gas-liquid-solid products of SS treatment in SCW
were investigated systematically. Furthermore, SS treatment in SCW in a short preheating and reaction time was
explored to determine the optimum treatment method and condition. This information is valuable for operating
parameters optimization of SS disposal in SCW.

2. Experimental section

2.1. Experimental apparatus and procedure

The high purity oxygen used as oxidant and helium used as an internal standard gas were all purchased from
Baoguang Gas Co., Ltd (Shaanxi Province, China). SS was taken from the Beishiqiao wastewater treatment plant
(Xi'an city, China). The concentration of SS was diluted to 8 wt.% with deionized water for experiments, because
this content can ensure continuous flow in the future application. Its physicochemical property is listed in Table 1.
Thus, its initial COD concentration was 73130 mg/L, and the ash content (dry basis) was 35.5 wt.%.
We used 4.4 ml mini-batch reactor with a high-pressure valve for the experiments. The reactor was purchased
from Shanghai Mian on Hay Hydraulic Equipment Co., Ltd. A certain amount of wet SS was loaded into the reactor
to ensure the same reaction pressure (24 MPa) at different reaction temperatures. The wet SS loadings were listed in
Table 2. The reactor was evacuated into a negative pressure with a vacuum pump, and then filled with helium. This
cycle was repeated three times to ensure reactor completely to be filled with helium, and the 0.1MPa (absolute
pressure) helium was served as an internal standard gas. Finally, oxygen was added into reactor, and its loading was
listed in Table 2 as well. OC was defined as follows:

the actual oxygen added (1)

OC =
the theoretical oxygen demand

The COD removal efficiency was calculated as follows:

COD - COD
COD removal efficiency (%) =
SS Liquid product
100% (2)
COD
SS

Table 1. Chemical characteristics of sewage sludge.

Moisture Ash Elemental analysis (wt.%)2 HHV COD
(wt.%)1 (wt.%)2 (MJ/kg) (mg/L)
C H N S O3
92 35.5 33.85 5.14 5.81 3.201 16.499 16.14 73130
1
On a received basis.
2
On air dry basis.
3
By difference (O% = 100% ash% C% H% N% S%).
 Guike Lin et al. / Energy Procedia 107 (2017) 357 362 359

The reactor was heated in a fluidized sand bath (Techne SBS-4), which has good thermal uniformity and highly
precise temperature control. The internal matters in the reactor were heated up to the desired temperature within
approximately 3 min. After the set residence time (7 min), we removed the reactor from the sand bath, and
immersed it into a cold water bath to interrupt the reaction, and then the reactor was connected to a gas analyzer.
After analyzing gaseous products, we slowly unscrewed the reactor to collect other reaction products. The reaction
products were further transferred into a centrifugal tube and centrifuged at 3000 r/min for 10 min. The aqueous
phase was transfer into a sample bottle by a pipette, then the solid phase was dried at 105 for 4 hours.

Table 2. SS and oxygen loadings at different temperatures.

Temperature SS Loading Theoretical oxygen Actual oxygen pressure demand (MPa)
() (ml) demand (mg)
OC=0 OC=0.4 OC=0.6 OC=1.0 OC=1.3
450 0.489 38.755 0 0.277 0.416 0.694 0.902
500 0.407 30.288 0 0.212 0.319 0.531 0.690

2.2. Analysis methods

A Mettler-toledo XA105 analytical scale with an accuracy of 0.01 mg was used to weigh the sample mass. A gas
chromatograph-mass spectrometer (GC-MS, Shimadzu Corporation QP2010 Plus) equipped with a Rtx-5 ms
nonpolar capillary column (30 m 0.25 mm 0.25 m) was adopted to analyze key compounds in the liquid phase,
in which helium was served as the carrier gas (1.0 ml/min). A mass spectral library and computer matching were
applied to facilitate compound identification. The gas-phase products were determined with a gas chromatograph
(GC, Beifen-Ruili, SP-3420A) equipped with a thermal conductivity detector (TCD). A 15-ft. 1/8-in. stainless
steel column (2.1 mm I.D.), packed with 60/80 mesh Carboxen-1000 (Supelco) separated each component using
argon (20 ml/min) as the carrier gas. The COD of the liquid phase was measured by a multi-parameter water
analyzer (NOVA60). A spectrophotometer (Shanghai Jinghua, UV-2000) was utilized to analyze the NH3-N content
of the liquid phase by a Nessler's reagent colorimetric method. A JSM-6390A (JEOL Ltd.) field emission scanning
electron microscope (SEM) equipped with energy dispersive spectroscopy (EDS) was employed to examine solid
residue structure and analyze its elemental composition.

3. Results and discussion

3.1. Gaseous products

Fig. 1 shows the influences of OC on gaseous products of SS disposal in SCW at 450 and 500 . Surprisingly,
gaseous products were mainly composed of CO2, CH4, CO, H2, N2 and a small amount of C2. The highest yield of
CH4 (1.6 mol/kg) and C2 (0.9 mol/kg) can be obtained at OC=0 and 500 . OC had a positive influence on the
yields of CO and C2 when OC changed from 0 to 1.3 at 450 for 7 min, while there was a strong negative
correlation between OC and the yields of CH4 and C2 at 500 . A possible reason is that the oxidant may contribute
to the oxidation reaction of combustible gases to form H2O and CO2 at high temperatures. One previous report also
found that the CH4 yield decreased when OC changed from 0 to 4 after SS treated in SCW at 450 [2]. Different
from previous investigation, the production of combustible gases at OC1.0 might be due to combustible gases and
oxygen incomplete reaction at short reaction time. In fact, the mole fraction of H2 initially increased and then
decreased with the increment of OC, and reached the highest value at OC=0.4. A small amount of oxidant increases
H2 yield but excess oxidant result in H2 yield decreased [8]. The N2 yield was higher in the presence of oxidant,
meaning that oxidant helped to convert N-containing compounds into N2 [2]. The consumption rate of oxygen from
SS disposal in SCW at 450 increased from 38.58 % to 68.03 % with OC increasing from 0.4 to 1.3. The CO2
yield and the oxygen consumption rate obviously increased with raising OC or temperature, suggesting that
oxidation reactions play a main role in CO2 formation at higher OC or temperature conditions.
360 Guike Lin et al. / Energy Procedia 107 (2017) 357 362

25
N2 C2 CH 4
20
H2 CO CO 2

Yield (mol/kg)
15

10

Reaction conditions

Fig. 1. Gas yields from SS disposal in SCW with different OCs at 450 and 500 .

3.2. Liquid products

Fig. 2 indicates the influences of OC on liquid products. As shown in Fig. 2a, it can be observed that the COD of
liquid phase initially increased and then decreased with the increment of OC, and reached the highest value at
OC=0.6. It suggests that the decomposition rate of organics in the liquid phase and the conversion rate of from SS
reached equilibrium at OC=0.6. Regardless of OC, the COD removal efficiency of liquid products from SS
treatment at 500 was generally higher than that at 450 , meaning that the reaction temperature had significant
effect on the decomposition of organics. The removal efficiency of COD from SS treatment in SCW at 500
increased from 76.25 % to 88.92 % with OC increasing from 0 to 1.3. In addition, the drop trend of COD at 450
or 500 after OC=0.6 is obvious with OC increasing, revealing that increasing OC is beneficial to SS treatment.
As displayed in Fig. 2b, the NH3-N concentration of liquid products firstly rose and then dropped with OC
increasing at 500 . Although the variation of the NH3-N concentration with OC increasing was complex at 450 ,
the NH3-N concentration at 450 and 500 was relatively close (within 500 mg/L) at the same OC condition.
The reason is that reaction temperature play a little role in reducing the NH3-N concentration in the tested
temperature range, which is consistent with previous investigation [9]. Certainly, NH3-N is an important
intermediate product of N-containing compounds with recalcitrant nature [10,11], and the decrease of the NH3-
N concentration was realized by the production and emission of N2 (see Fig. 1) and the production of other N-
containing compounds. It is interesting to find that the NH3-N concentration reached the highest value at OC=0.6
and 500 , while it reached the highest value at 450 at OC=1.3. The possible reason is that NH3-N is difficult to
be oxidized at relatively low reaction temperature, and this phenomenon has been found in previous research [2].
Apparently, high temperature and OC help to NH3-N removal of liquid products.

50000 100
(a) 4400
450 500 450 500 (b) 450 500
90
COD removal efficiency (%)

40000 4000
80

70 3600
NH3-N(mg/L)
COD (mg/L)

30000
60 3200
20000
50
2800
40
10000 2400
30
2000
0 20 0 0.4 0.6 1 1.3
0 0.4 0.6 1 1.3
OC OC

Fig. 2. Influences of OC on liquid products at 450 and 500 : (a) COD and its removal efficiency; (b) NH3N concentration.

On the basis of GC-MS analysis of the liquid phase, major compounds and corresponding retention times and
peak areas are listed in Table 3. Obviously, most of compounds disappeared at OC=1.0 as temperature changed from
450 to 500 C, meaning that increasing temperature is beneficial to the decomposition of organics in SS. The main
products of liquid seem to be diethyl phthalate and phenols. The fraction of diethyl phthalate changed dramatically
 Guike Lin et al. / Energy Procedia 107 (2017) 357 362 361

from 40.8 % (peak area) to 62.59 % in the liquid phase due to its stubborn features [12,13].

Table 3. GC-MS analysis results of liquid products.

Retention Peak Area (%)

NO. Compounds
time 450 , OC=1.0 500 , OC=1.0
1 30.059 Butylated Hydroxytoluene 5.08 -
2 30.065 2,4,6-Tris(1,1-dimethylethyl)-4-methylcyclohexa-2,5-dien-1-one - 6.16
3 32.659 Fluorene 15.70 -
4 33.364 Diethyl Phthalate 40.80 62.59
5 57.222 Nonane, 5-methyl-5-propyl- 1.71 -
6 59.989 3,5-Dimethyl-4-octanone 2.74 -
7 60.464 Phenol, 2,2'-methylenebis[6-(1,1-dimethylethyl)-4-methyl- 20.90 17.09
8 62.649 Tridecane, 1-iodo- 2.42 -
9 77.204 Heptasiloxane, hexadecamethyl- - 1.21
10 83.327 Arsenous acid, tris(trimethylsilyl) ester 1.67 -

3.3. Solid products

Fig. 3 shows the surface morphology of SS (dry basis) and solid residue from SS treatment in SCW. The surface
morphology of dry basis SS displayed bright and smooth laminar structure, while solid residue exhibited gray color
and loose surface with tiny particles. With OC rising, solid residue had more loose surface structure and smaller
particle size. It implies that high OC could increase the decomposition of organic matters in SS. Their semi-
quantitative EDS analysis were further provided in Fig. 4, and they just were acted as auxiliary judgment for
element components [14]. Thus, the variation trend of major elements can be seen clearly through the EDS results.
The content of C had a significant decrement with the increment of OC. However, the contents of some elements
(such as Si, Al and Ca) in solid residue were almost double compared with those in dry basis SS, showing that the
enrichment of inorganic matters due to the decomposition of organic matters.

Fig. 3. Surface morphologies of (a) SS (dry basis) and solid residue in SCW at (b) 450 , OC=0.4; (c) 450, OC=0.6; (d) 450, OC=1.0.

60
(a) (b) (c) (d)
50
Element content (wt.%)

40

30

20

10

0
C O Al Si Ca
Main element

Fig. 4. EDS analysis results of (a) SS (dry basis) and solid residue in SCW at (b) 450 , OC=0.4; (c) 450 , OC=0.6; (d) 450 , OC=1.0.
362 Guike Lin et al. / Energy Procedia 107 (2017) 357 362

4. Conclusions

We systematically investigated the influences of OC on gas-liquid-solid products of SS treatment in SCW, and

some valuable information was obtained. CO2 yield obviously increased with raising OC or temperature, and
oxidant helped to convert N-containing compounds into N2. A small amount of oxidant increased H2 yield but
excess oxidant might result in H2 to form H2O. OC had significant effect on the COD removal efficiency and the
NH3-N concentration of liquid products. High OC and temperature help to COD removal of liquid products.
The NH3-N concentration reached the highest value at OC=0.6 and 500 , compared with at OC=1.3 and at 450 C.
Diethyl phthalate was main stubborn substances in the liquid phase when SS was treated at OC=1.0 and 500 C. The
contents of some elements (such as Si, Al and Ca) in solid residue were almost double compared with those in dry
basis SS. In the future, the removal of the stubborn substances (such as diethyl phthalate and phenols) in the liquid
phase should be paid attention.

Acknowledgements

This work is supported by the Projects from National Natural Science Foundation of China (No. 21576219), the
Special Financial Grant from the China Postdoctoral Science Foundation (NO.2014T70922), the Fundamental
Research Funds for the Central Universities, the National Science Foundation for Post-doctoral Scientists of China
(No. 2013M540748), and the Special Financial Grant from the Shaanxi Province Postdoctoral Science Foundation.

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