Sie sind auf Seite 1von 9

Chemical Engineering Journal 269 (2015) 343351

Contents lists available at ScienceDirect

Chemical Engineering Journal


journal homepage: www.elsevier.com/locate/cej

A new system design for supercritical water oxidation


Zhong Chen a,b,c, Guangwei Wang a,b,c, Fengjun Yin a,c, Hongzhen Chen a,c, Yuanjian Xu a,c,
a

Chongqing Institute of Green and Intelligent Technology (CIGIT), Chinese Academy of Sciences, Chongqing 400714, PR China
Key Laboratory for Solid Waste Management and Environment Safety, Ministry of Education of China, Tsinghua University, Beijing 100084, PR China
c
Key Laboratory of Reservoir Aquatic Environment, Chinese Academy of Sciences, Chongqing 400714, PR China
b

h i g h l i g h t s

g r a p h i c a l a b s t r a c t

 A lab-scale SCWO system based on

DGSWR was described in detail.


 Gas seal of DGSWR was veried under

supercritical conditions.
 Sewage sludge with 2.6211.78% DS

was safely treated.


 Gravity sedimentation of solids

partially achieved.

a r t i c l e

i n f o

Article history:
Received 6 December 2014
Received in revised form 29 January 2015
Accepted 3 February 2015
Available online 11 February 2015
Keywords:
Anti-corrosion
Anti-plugging
System design
Dynamic gas seal wall reactor
Supercritical water oxidation

a b s t r a c t
As the main obstacles for the industrialization of supercritical water oxidation (SCWO) technology, corrosion and plugging are mostly occurring in the high pressure high temperature (HPHT) sections, including preheater, reactor, heat exchanger and cooler. In this paper, a lab-scale SCWO system based on
dynamic gas seal wall reactor (DGSWR) has been described, tested and discussed in detail. The results
showed that the preheating problems of waste with high solid content has been solved and the gas seal
of DGSWR has been successfully veried under 2829 MPa and around 400 C. Sewage sludge with
2.6211.78% dry solid has been degraded and the COD removal efciency can reach up to 99.15%. However, the solid particle sedimentation was only partly achieved. According to the results analysis, based
on the Stokes Law, both small particle size and counter-current of upward reaction medium and downward solids are responsible. Future improvements for the SCWO system were also discussed at the end of
this article.
2015 Elsevier B.V. All rights reserved.

1. Introduction
For environmental awareness, water is undoubtedly the optimal reaction medium. But at room temperature, the reaction is
too slow for most redox reactions, especially for the destruction
Corresponding author at: Environmentally-Benign Chemical Process Research
Center, Chongqing Institute of Green and Intelligent Technology, Chinese Academy
of Sciences, No. 266 Fangzheng Avenue, Shuitu Hi-tech Industrial Park, Shuitu
Town, Beibei District, Chongqing 400714, PR China. Tel.: +86 23 65935819.
E-mail address: xuyuanjian@cigit.ac.cn (Y. Xu).
http://dx.doi.org/10.1016/j.cej.2015.02.005
1385-8947/ 2015 Elsevier B.V. All rights reserved.

of organic wastes. One of main reasons is the solubility in water


for both organic waste (mostly nonpolar) and oxidant (mostly
oxygen) are very low at room temperature. Interestingly, this property is overturned in supercritical water (SCW, Tc = 373.946 C,
Pc = 22.064 MPa [1]), which can be completely miscible with
organic compounds and oxygen [2]. Besides, SCW also possess
other unique properties [2,3], such as high diffusivity and density,
low viscosity and inorganic solubility. Supercritical water oxidation (SCWO) is a redox reaction to destroy organic compounds in
SCW with the participation of oxidant (such as air, oxygen and
hydrogen peroxide etc.) [2]. In general, most of organics can be

344

Z. Chen et al. / Chemical Engineering Journal 269 (2015) 343351

nearly completely degraded by SCWO in less than 1 min [3], and


the products are the environmentally acceptable efuents, such
as H2O, CO2, and N2 etc. [4]. As the excellent merits, the SCWO
has been hailed as an emerging and environmentally-benign technology for the treatment of various hazardous wastes in the last
three decades [4,5].
The SCWO, as such a great potential technology, its commercial
development is actually far lag behind the expectation. Most of the
full-scale commercial plants have been shut down and only two of
them are in operation as of January 2012 [6]. Corrosion and plugging are the main obstacles [27]. To overview the typical SCWO
process (Fig. 1), it can be found that both corrosion and plugging
are mainly occurring in the high pressure and high temperature
(HPHT) sections, and the details are discussed as fellow:
1.1. Preheaters
The oxidant preheater can be slightly corroded in the presence
of water, such as the wet air without dehydration. The ion product
of water will maximize under subcritical conditions, which will
lead to corrosion problems in both pure water preheater and aqueous waste preheater [810]. Some salts dissolved in the waste
stream will precipitate out with the increasing of temperature
[10] and some organic compounds in the aqueous waste will polymerize in the absence of oxidant [3,10]. Both of salt precipitation
and polymerization may lead to plugging problems in waste
preheater.
1.2. Reactor
The heteroatoms (S, Cl, P, N, etc.) contained in the organic waste
will be dissociated to form corresponding acids in reactor. The
SCWO reactor, where is a harsh chemical and physical environment of presence of acids, high concentration of oxidant, high temperature and high pressure, should undergo severe corrosions [8
10]. The inorganic salts for several reasons [7] would like to precipitate from SCW to scale on the surface of reactor and leads to
severe plugging problems.
1.3. Cooler and heat exchanger
Same as in the process of preheating, the cooling and heat
exchanging should undergo the subcritical conditions, under
which the corrosion of water is much higher [8]. The efuents
containing various acids, if without neutralization, will lead to

severe corrosion in cooler and heat exchanger, which is more


severe than that in reactor [810]. Part of salts failed to separate
in reactor will also result in plugging problems in cooler and heat
exchanger.
So far, a super material that can withstand all corrosion conditions in SCWO has not yet been reported [8]. If any, the plugging
and others problems will also hinder the development of SCWO.
Therefore an appropriate system design for SCWO is necessary.
In this paper, the focus of anti-corrosion and anti-plugging has
been expanded from reactor to the whole HPHT sections (see
Fig. 1). A novel reactor concepts named as Dynamic Gas Seal Wall
Reactor (DGSWR) [11] was adopted, which was optimized from
Transpiring Wall Reactor (TWR) and was designed to handle
the reactor corrosion and plugging problems. A technology of
multi-feed injection was designed to handle the waste preheating
problems. A lab-scale SCWO device based on this novel design was
manufactured and tested under 2829 MPa around 400 C.

2. A new SCWO system design


A new SCWO system with a maximum treatment capacity of
2 kg h1 at 15% dry solids (DS) has been designed in CIGIT based
on the preliminary researches [11,12]. The system was particularly
descripted in the following four parts as illustrated in Fig. 2.

2.1. Reactor design


As the heart of SCWO, reactor always suffers from both corrosion and plugging. Several types of reactors have been invented
to handle these problems. The related reviews can be found in literatures [2,79,13]. The DGSWR was adapted in the new system.
The basic structure of DGSWR is the same as that of a TWR: a double wall reactor consists of outer pressure bearing wall and inner
transpiring wall (also named as porous wall). Transpiring uid lls
the annulus between the two walls and continuously ows
through the transpiring wall to form a protective lm on the inner
surface of transpiring wall. The protective lm is a mobile surface
and can protect transpiring wall from corrosion and salt deposition
[2]. Pure water was used as the transpiring uid in TWR and was
replaced by air in DGSWR, which is the essential difference
between these two types of reactors. Based on the special physical
properties of air, DGSWR can enhance the anti-corrosion and
anti-plugging of TWRs and to avoid the demerits of TWRs. The feasibility of DGSWR has been proved in previous research [11].

Fig. 1. Typical SCWO process. Adapted from literatures [8,9].

Z. Chen et al. / Chemical Engineering Journal 269 (2015) 343351

345

Fig. 2. Schematic diagram of the new SCWO system.

Two of the same units named as Reaction Vessel 1 and Reaction


Vessel 2 (see Fig. 2) were connected by Flange (see Fig. 3) to constitute the reaction area of the new system. Both of them are the
type of DGSWR. Each unit with height of 500 mm consists of pressure bearing wall and porous wall. The pressure bearing wall with
inner diameter of 45 mm was made of 316L stainless steel and can
withhold a pressures up to 50 MPa. The porous wall is the type of
sintered wire netting [14] and made from 316L stainless steel. It
was made of outer 32 oors nets with pore size of 2  105 m
and inner 5 oors nets with pore size of 5  106 m. Its inner diameter and thickness are 29.5 mm and 5 mm, respectively.
In the new system design, air is not only the oxidant but also
the transpiring uid of DGSWR. The air must ow through the porous wall and mix with wastes in reaction area, and then the reaction would happen. Therefore, the sooner they mix the better. The
preliminary research [11] indicates that the transpiring uid tends
to ow through the porous wall around the transpiring uid inlet
section and upper section of porous wall. Based on the characteristic of DGSWR and the transpiring uid dynamics aforementioned, a
pair of symmetrical air inlets with inner diameter of 2 mm was set
at the lower section of each reaction vessel (see Fig. 2). The

Fig. 3. Picture of the Flange connecting Reaction Vessel 1 and Reaction Vessel 2.

distances from the bottom to inlets are 50 mm for Air 1 and


110 mm for Air 2, respectively.
Air was supplied by Air Compressor B (Atlas, GX4FF-10) and
was divided into two branches, Air 1 and Air 2. Air 1 was delivered
into Reaction Vessel 1 by Booster Pump B and the ow rate was
controlled by Flow meter B from SEVENSTAR (D07-9E) with measuring range from 0.00 to 8.33  104 m3 s1 (standard conditions). Air 2 was delivered into Reaction Vessel 2 by Booster
Pump A and the ow rate was controlled by Flow meter A from
SEVENSTAR (D07-7B) with measuring range from 0.00 to
1.67  104 m3 s1 (standard conditions). Both booster pumps
(STT60AL, Shineeast) were driven by Air Compressor A (Atlas,
GXe11FF-10). The feasibility analysis of DGSWR suggests that air
in low temperature has a better performance on the gas seal
and the heat capacity of air is much lower than that of water
[11], therefore the air was not preheated in the new system. In consideration of the high energy consumption in start-up and the heat
dissipation during operation, each reaction vessel was equipped
with a heating jacket with maximum power of 3 kW.
2.2. Multi-feed injection
Besides the reactor, waste preheater is also vulnerable to attack
by corrosion and plugging. In addition, it is not easy to pump multiphase wastewater over a pressure of 22.1 MPa, such as oilwater
mixture and oilwatersolid mixture. Several full scale SCWO
plants have been shut down due to these reasons [6].
Hydrothermal ame, which was rst reported in 1986 by E.U.
Franck from University of Karlsruhe [15], is one of the effective
methods to solve the preheating problems. Auxiliary fuel (such
as isopropyl alcohol, methanol, etc.) is injected into SCWO reactor
through a special device and burn with oxidant. The ame with
temperature of typically over 1000 C is a heat source and then the
waste water can be fed at subcritical temperature or even room
temperature [3]. This technology has been applied in several types
of SCWO reactors in the last two decades [1621].
Oxygen multi-injection developed in CNRS of France is another
effective way [22]. Waste water was fed at subcritical or near-critical temperature and oxygen was injected through three inlets
along the tubular reactor [2325]. The temperature of mixture

346

Z. Chen et al. / Chemical Engineering Journal 269 (2015) 343351

increases along the length of reactor as the reaction is exothermic,


and the critical point of water is overcome in reactor rather than in
preheater (like most designs). This design can reduce the energy
consumption of preheating and makes the control of thermal agitation easy [3]. And by coincidence, both of preheating at low temperature (less than 350 C [26]) and presence of oxidant avoid the
polymerization of organics in waste water. The corrosion of subcritical water and the polymerization of organics are the main reasons of operation problems in waste preheater and may be avoided
by this design.
Vadillo and coworkers from University of Cadiz in Spain
reported a new feed system for multiphase wastewater in SCWO
[26]. A non-aqueous waste with no preheating and an aqueous
waste over 400 C ware pumped independently and mix at the
beginning of reactor to form a supercritical homogeneous phase.
The new feed system, which can avoid the problems of pumping,
preheating and thermal control, is another candidate.
Based on the advantages of above technologies (hydrothermal
ames [16], oxygen multi-injection [22] and new feed system
[26]), a new methods named as multi-feed injection was designed
in the new SCWO system, as shown in Fig. 2. Stream 1 (aqueous
waste or water with fuel) is pressurized by Pump C and preheated
by Heat Exchanger, Preheater C and Preheater B in turn, and nally
introduced into the Reaction Vessel 1 in the bottom. The inlet temperature of Stream 1 (T2 in Fig. 2) is over 500 C typically. Stream 2
(e.g., sewage sludge, oil waste, etc.) was stored in Tank A and Tank
B and one operates after the other, alternatively. Water is delivered
by Pump A to drive the piston in Tank A or Tank B and then the
waste is extruded out into Preheater A, and eventually introduced
into Reaction Vessel 1 on the top. The inlet temperature of Stream
2 (T3 in Fig. 2) ranges from room temperature to 350 C depended
on the type of waste. Due to gravity, Stream 2 with a higher density
ows down and mixes with upward Stream 1 in the Reaction Vessel 1. Part of the waste is oxidized in Reaction Vessel 1 and the rest
is further degraded in Reaction Vessel 2.
Pump A (2J-X 2/50) with maximum pressure of 50 MPa and
rated ow of 2 L h1 was purchased from Hangzhou Zhejiang Petrochemical Equipment CO., LTD, China. The effective volume of
each tank (Tank A and Tank B) with inner diameter of 95 mm is
2.5 L. Preheater A with maximum power of 4 kW was designed
as a single straight tube heater to avoid some blind spaces and to
reduce the ow resistance. The length and inner diameter of the
tube are 750 mm and 8 mm, respectively. As shown in Fig. 3, the
inlet and distributor with the same inner diameter of 8 mm are
set on the ange and the Stream 2 would be dispersed by the
distributor.
Pump C (2J-X 4/50) was supplied by the same manufactory as
Pump A and the rated ow is 4 L h1. The two preheaters for
Stream 1 are both the type of coil electric heater. The maximum
power is 4 kW for Preheater B and 3 kW for Preheater C. Each heater was made of a single tube with inner diameter of 8 mm and
length of 6.5 m.
2.3. Gravity sedimentation
To avoid plugging, one of the dominant technologies is the
reverse ow reactor with a brine pool [7]. Salts precipitated in
supercritical zone (upper section of reactor) will fall down to the
subcritical zone (lower section of reactor) and re-dissolve in
quench water [13,14], and then the salts can be removed by brine
efuent. Only for the salt separation purposes (without waste oxidation), the recovery of this design can reach up to 97% for type 1
salts [27], 95% for type 2 salts and mixtures of two salts [28]. But
for degradation of salt containing waste water, the efciency is
only 65% [29], 555% [30] and even much lower [31]. It must be
noted that the waste water in these researches [2731] is articial

and the salts is the type of sticky salts that has good water-solubility. But many potential SCWO applications (such as sewage sludge,
oily sludge and so on) contents not only sticky salts, but also nonsticky solid [2]. The non-sticky solid cannot be dissolved by the
quench water and will lead to plugging problems in following
units, such as heat exchanger, cooler and so on.
The new design in this paper intends to separate both sticky
salts and non-sticky solid. The mixture of salts and solids are
designed to be settled by gravity and stored in the Solid Collector
(see Fig. 2), batched emptied. The Solid Collector with a length of
300 mm has the same inner diameter as pressure bearing wall,
and the effective volume is 0.45 L.
As shown in Fig. 2, a Condenser was set up to quench the efuents from Reaction Vessel 2. The basic structure of the Condenser is
as same as the Reaction Vessel units. There is only one inlet with
inner diameter of 2 mm in the middle of Condenser. Quench Water
was delivered by Pump B that is exactly the same as Pump A.
Besides cooling, the Condenser can separate salts and solids that
failed to settle in Solid Collector. On one hand, the sticky salts will
re-dissolve in the quench water; on the other hand, the non-sticky
solid particles tend to be captured by the subcritical water and
stored in the Condenser. Such design tries to enhance the effect
of gravity sedimentation and to avoid the plugging problems in
heat exchanger and cooler.
2.4. Heat recovery and pressure control
In order to achieve a self-sustaining running, heat exchanger
was always used to recovery the heat of efuents. This method
was also adapted in the new SCWO system. As shown in Fig. 2,
the Efuent was cooled in Heat Exchanger and Cooler, in turn. Both
Heat Exchanger and Cooler are type of single double-pipe. The
effective heat-exchanging surface is 9.11  103 m2 for Heat
Exchanger and 1.53  102 m2 for Cooler.
Eleven K-type thermocouples with range from 0 to 800 C were
adapted to measure the temperatures and the exact positions were
shown in Fig. 2. In order to protect thermocouple from corrosion, a
tube with inner diameter of 2 mm was equipped for each thermocouple (T1T4, T10T11, see Figs. 1 and 2), and one single tube with
inner diameter of 4 mm was equipped for thermocouples of T5T9.
They are evenly spaced for T5T9 and the distance of two neighboring positions is 100 mm.
The system pressure was controlled by a back pressure valve as
usual designs. In order to avoid operation problems caused by solids in efuent [3], a Filter with pore size of 5  105 m was placed
between Cooler and Pressure Control (see Fig. 2). The solid particles failed to separate will be captured by the Filter. So the other
function of the Filter is to check the separation efciency of gravity
sedimentation.
3. Experimental tests and results
Sewage sludge from Xiaojia River wastewater treatment plant
in Chongqing was selected as the typical waste in the tests. The
properties of the sewage sludge are shown in Table 1. The ash of
sewage sludge is 45.53% of its dry mass. In order to increase the
uidity, the sewage sludge with an initial solid content of 19.73%
DS was diluted to 2.6211.78% DS. The diluted sewage sludge is
the Stream 2 in the tests of the new SCWO system.
As most methods, isopropanol was added as the co-fuel [32] in
this paper. The aqueous of isopropanol or de-ionized water was
used as feedstock of Stream 1. The concentrations of isopropanol
in the aqueous ranged from 0.0 wt.% to 3.0 wt.%. Five experiments
were carried out in the study and operation conditions were shown
in Table 2.

347

Z. Chen et al. / Chemical Engineering Journal 269 (2015) 343351


Table 1
Properties of the sewage sludge.
Properties

Values standard deviation


of three replicates

Dry solids (DS, 105 C, wt.% wet mass)


Ash content (815 C, wt.% dry mass)

19.73 0.12
45.53 0.10

Elemental analysis (wt.% dry mass)


C
H
N
S
Others (rest to 100%)
TOC (g C kg1 dry mass)

28.05 0.13
4.77 0.11
4.57 0.01
0.80 0.06
61.81
241 2

3.1. Operation results


In general, a complete operation process includes the following
steps: pressurizing, heating, pumping Stream 1, pumping Stream 2,
sampling, depressurizing and cooling. The temperatures of the
SCWO system was adjusted timely by switching on and off the Preheating A, B, C and heating jackets of reactors. Table 3 exhibits the
pressures and temperatures under steady state of each operation
conditions. In addition, the operation processes of Exp. 1, Exp. 3
and Exp. 5 were recorded in details, and the temperatures variation
curves are shown in Figs. 46, respectively.
To preheat sewage sludge directly from room temperature to
supercritical condition will lead to plugging problems. Yin et al.
[33] suggest the preheating temperature should be no more than
200 C, under which the sewage sludge maintains good uidity.
Hence, the inlet temperature of Stream 2 (T3) in this study was controlled below 200 C (see Table 3). According to operation steps,
the SCWO system would be preheated to supercritical conditions
before pumping Stream 2, which leads to the location of T3 was
also warmed up to over 300 C during heating step. As shown in
Figs. 46, the T3 will decrease to appropriate temperature ranges
while the sewage sludge was pumped into reactor. But it must
be pointed out that an interrupt or a low ow rate of Stream 2 will
increase the risk of plugging at the position of T3 because both of
them will result in temperature rise of T3. Therefore, a steady
Stream 2 with a mass ow rate of over 0.5 kg h1 is necessary in
the new SCWO system.
As shown in Figs. 46, T1, T4 and T5T11 (except T2 and T3) have
gone up after pumping Stream 2. While reaching steady state, the

Fig. 4. Temperature variation curves of Exp. 1. Where, (a) start to pressurize; (b)
start to heat system; (c) start to pump Stream 1 (3.0 wt.% isopropanol); (d) start to
pump Stream 2 (sewage sludge at 2.62% DS); (e) switch Stream 1 from isopropanol
aqueous to pure water.

temperature of low inlet section is higher than that of upper outlet


section in Reaction Vessel 1, and the temperature of middle section
is the highest in Reaction Vessel 2 (see Table 3). Such temperature
distribution was caused by feeds inlet temperatures, heating jackets and heat dissipation. The temperature of Stream 1 dropped
from 572597 C (T2) to 385454 C (T1) by the cooling of Air 1
(which was not preheated) and heat dissipation of Solid Collector
(no heating jacket installed). In Reaction Vessel 1, Stream 1 of
385454 C mixes with Air 1 of room temperature and Stream 2
of 149188 C, which leads to T1 > T4. The exothermic reaction of
sewage sludge leads to the T1 increased about 50 C at the moment
of about 80 min after feeding Stream 2, as shown in Figs. 46. In
Reaction Vessel 2, the mixture from Reaction Vessel 1 was cooled
by Air 2 and the top area was cooled due to heat dissipation, which
causes T5  T6 < T7  T8 > T9.
There is an interesting phenomenon in Exp. 1 that T3 sharply
rose about 100 C and the T1, T4T11 decreased slightly about
27 C when switching Stream 2 from sewage sludge (2.62% DS)
to pure water at same ow rate, as shown in Fig. 4. This indicates
the pyrolysis of sewage sludge (preheating) is an endothermic
reaction and the SCWO of sewage sludge is exothermic.

Table 2
Operation conditions.
Exp.

1
2
3
4
5

Stream 1 (sewage sludge)

Stream 2 (water and isopropanol)

Air

Solid
content
(% DS)

Mass ow rate
(kg h1)

Isopropanol
concentration
(wt.%)

Mass ow rate
(kg h1)

Mass ow rate of Air


1 (kg h1)

Mass ow rate of Air


2 (kg h1)

2.62
2.90
3.18
8.55
11.78

2.10
0.65
1.48
0.84
0.78

3.0
1.0
2.0
0.0
0.0

1.81
0.56
1.38
1.34
2.81

0.26
0.27
0.25
0.25
0.25

0.33
0.34
0.33
0.31
0.34

Stoichiometric
oxygen excess

COD removal
efciency (%)

0.73
3.97
1.14
1.68
1.49

84.02 c
99.15
90.83
97.70
95.76

Table 3
Pressures and temperatures of SCWO system under steady state of each operation conditions.
Exp.

P (MPa)

T1 (C)

T2 (C)

T3 (C)

T4 (C)

T5 (C)

T6 (C)

T7 (C)

T8 (C)

T9 (C)

T10 (C)

T11 (C)

1
2
3
4
5

28.9
28.5
28.8
29.2
28.3

454
385
445
414
394

588
572
596
597
576

149
172
188
176
185

383
373
387
394
400

371
362
376
379
386

370
375
374
378
387

377
387
382
394
396

380
381
381
397
394

365
354
357
383
372

333
284
316
311
329

275
154
235
205
236

348

Z. Chen et al. / Chemical Engineering Journal 269 (2015) 343351

Fig. 7. Images of sewage sludge and efuents in Exp. 5.

Fig. 5. Temperature variation curves of Exp. 3. Where, (a) start to pressurize; (b)
start to heat system; (c) start to pump Stream 1 (2.0 wt.% isopropanol); (d) start to
pump Stream 2 (sewage sludge at 3.18% DS).

Fig. 8. Images of liquid products. No. 15 correspond to Exp. 15, respectively, and
No. 6 is the de-ionized water.

Fig. 6. Temperature variation curves of Exp. 5. Where, (a) start to pressurize; (b)
start to heat system; (c) start to pump Stream 1 (pure water); (d) start to pump
Stream 2 (sewage sludge at 11.78% DS).

During the study, it was found that the heat dissipation of Condenser is very signicant because there was no heat preservation
equipment installed. So the quench water was not necessary and
not delivered for all experiments. Part of waste heat of efuents
with temperature range of 284333 C (T10) was recovered by
the Heat Exchanger, the Stream 1 can be preheated from room
temperature to 154275 C (T11).
Sewage sludge was degraded to almost transparent liquid product and brick-red solid product by the new SCWO system, as
shown in Fig. 7. Almost all of the solids is the type of non-sticky
solid and come from sewage sludge (Stream 2). The liquid products
of the ve experiments are exhibited in Fig. 8, where the appearance of No. 2 is nearly the same as that of de-ionized water. The
chemical oxygen demand (COD) removal efciency range of
84.0299.15% was listed in Table 2, which is lower than that of literature reports [3,5]. Two factors are responsible. One is the low
reaction temperature due to heat dissipation and low inlet temperatures of air and sewage sludge. Temperature signicantly impacts
the COD removal efciency in SCWO. For most SCWO, operation

temperature is around 500 C which is much higher than 400 C


of this study. The other one is the low oxygen excess, as listed in
Table 2. According to the kinetic model of waste oxidation under
hydrothermal conditions, the reaction order for oxygen is 01
[34,35]. M. Goto et al. [36] proposed the reaction order for oxygen
is 0.51 under subcritical condition because of the existence of gas
and liquid phases, and is zero under supercritical condition as the
single phase. In addition, the oxygen is in excess for most SCWO.
Therefore, the oxygen was considered as an independent factor
on the COD removal efciency by most SCWO researches. However, the inuence of oxygen cannot be ignored in the new SCWO
system. Phases interface occurred in the reaction area because the
air was delivered at room temperature. Besides, the oxygen
excesses are only 0.731.68 except Exp. 2 as shown in Table 2.
These can explain the COD removal efciency increases with the
air excess, as shown in Table 2.
As shown in Fig. 2, both of Booster Pump A and B were drove by
Air Compressor A. The insufcient force results in that the total
mass ow rate of Air 1 and Air 2 is only in the range of 0.56
0.61 kg h1 under 28.529.2 MPa. Besides, adding isopropanol as
co-fuel aggravated the lack of oxidant. As shown in Tables 2 and
3, isopropanol did not signicantly improve the reaction temperatures, but consumed signicant amount of oxidant. Results of Exp.
4 indicate that Stream 1 (pure water without isopropanol) can
achieve appropriate reaction temperatures at a mass ow ratio of
1.6 times of Stream 2. So pure water with inlet temperature of over
550 C, by contrast with isopropanol aqueous, is more economic
and practical in the new SCWO system.

Z. Chen et al. / Chemical Engineering Journal 269 (2015) 343351

3.2. Gas seal performance

349

Solids C), and remaining about 35% scaled on the inner surface of
porous walls, Flange and somewhere else.
The particle sizes (dp) of Solid A, Solid B and Solid C were measured by Rise-2008 laser particle size analyzer and the results are
shown in Fig. 10. The particle size range from 0.10  106 m to
4.00  106 m and the average diameters of Solid A, Solid B and
Solid C are 0.93  106 m, 0.90  106 m and 0.77  106 m,
respectively.
When Rep < 2, the sedimentation of solid particle can be
described by Stokes Law [37]:

The most important design point of the new SCWO system was
the gas seal. The preliminary research [11] demonstrated that
this design was feasible, so one of the purposes for this study
was testing the gas seal performance of DGSWR under real SCWO
conditions. After experiments were nished, imagines of pressure
bearing walls and porous walls were captured, as shown in
Fig. 9. It can be seen that no solids particles deposit on the surface
(both inner surface of pressure bearing wall and outer surface of
porous wall) except the locations around air inlets, and the amount
of particles is much more in Reaction Vessel 2 than in Reaction
Vessel 1. Such phenomena can be explained by the pumping conditions of air streams. As the pulse nature of ow rate of booster
pumps, the reaction mixtures around the air inlets were perturbed,
which results in part of solids was rushed out of the porous wall.
And higher the air mass ow rate, more violent the turbulence.
The ow rate of Air 2 is 1.36 times of that of Air 1 (see Table 1),
which is the reason of more solids particles seen in Reaction Vessel
2. Look it the other way, if gas seal is not working under supercritical condition, there should be solid deposits seen all around
the reaction vessel, especially at the end away from the air inlet
because the air ow is slower at that end as compared to the air
inlet end. Now only slight solid deposits can be seen at the air inlet
end in this study. So the gas seal should be working. The slight
solid deposits around the air inlet is most likely been blown
out by the air pulse.
To sum up, the effect of gas seal has been veried under real
SCWO conditions and a serious pulsating air stream will break this
function at the area around air inlet. So a smoother and isotropicdispersed air stream is necessary.

where, the l and q are the viscosity (Pa s) and density (kg m3) of
reaction medium, respectively. In this paper, the reaction medium
can be considered as the mixture of Stream 1, Stream 2, Air 1 and
Air 2. The qp is the true density of solid particles, 2537 kg m3.
The g is the constant of gravitational acceleration, 9.81 m s2. The
Rep is the particle Reynolds number and expressed by Eq. (2):

3.3. Gravity sedimentation performance

The new design intended to settle solid particles by gravity and


store in Solid Collector, but the results indicated such design has
only achieved partial success. The result of Exp. 5 showed that only
about 30% of solid particles was captured in Solid Collector (named
as Solids A), about 23% was captured by Condenser (named as Solids B), about 12% was carried out by efuents stream (named as

where, the Q is mass ow rate of reaction medium, kg h1. The A is


cross sectional area of the porous wall, 6.8  104 m2.
In order to simplify the calculations, both Stream 1 and Stream
2 are considered as pure water, and all the feeds (Stream 1, Stream
2, Air 1 and Air 2) are injected at once in the bottom of Reaction
Vessel 1.
The l and q of reaction medium were calculated by Eq. (5) [38]:

ut

dp qp  qg
18l

dp up q

Rep

As shown in Fig. 2, the reaction medium in reaction vessels


ows upward with a velocity of u (m s1), and the solid particles
moves down by gravity with a settling velocity of ut (m s1). Thus,
the apparent velocity (up, m s1) of particles dened as Eq. (3):

up u  ut

When up > 0, the particles will be carried out by the reaction


medium; on the contrary, the particles will move downward when
up < 0. The u in Eq. (3) is dened as Eq. (4):

Q =q
3600A

n
X

vi Y i

Fig. 9. Images of pressure bearing walls and porous walls after Exp. 5, without any
cleaning.

Fig. 10. Particle size distribution of solids in Exp. 5.

350

Z. Chen et al. / Chemical Engineering Journal 269 (2015) 343351

However, there are also some shortcomings in the new SCWO


system. The most obvious one is solid precipitation due to the
counter-current of upward reaction medium and downward solid
particles. The structure of the SCWO system should be adjusted
to insure that the reaction medium and solid particles will form
as a co-current ow rather than a counter-current ow. Both stability and ow rate of air stream are insufcient, which leads to
lose efcacy of gas seal and low oxygen excess, respectively. The
air mass ow rate should be increased and air stream should be
pumped smoothly and isotropic-dispersed. Besides, enhancing
heat preservation is also necessary. All the aforementioned
improvements will be investigated in future.

Acknowledgments

Fig. 11. Calculation results of solids apparent velocity versus solids diameter under
Exp. 5 conditions.

where, the transport properties of the mainstream (Y) are the mass
average of corresponding pure component properties (Yi). The viscosity and density of pure uids (water, oxygen and nitrogen) were
obtained from the NIST database [39].
The apparent velocity (up) of solid particle with a diameter (dp)
range of 0.10  1061.50  105 m has been calculated under the
operation conditions of Exp. 5. All the calculated results satised
Rep < 2, which suggest the settling velocity of particles is a creeping
ow. As shown in Fig. 11, the up < 0 when the particle size is over
the critical diameter (1.36  105 m), which signify only the solid
particle with a diameter of over 1.36  105 m can be settled by
gravity under Exp. 5 operation conditions.
The calculation result is not fully accordant with the experimental result, which is due to the simplication. Under the real
conditions, on one hand, the feeds of Stream 1, Stream 2, Air 1
and Air 2 were injected at multiple points in the new SCWO system
(see Fig. 2). The actual ow rate (Q) was less than the total mass
ow rate of reaction medium and the uid state in reactor was
complex and probably a turbulence ow, rather than a creeping
ow. On the other hand, some of solid particles would aggregate
to form larger particles. According to Eqs. (1), (3) and (4), both
lower Q and bigger dp will promote the gravity sedimentation of
solid particles. Hence, the counter-effect of upward u and downward ut on the solid particles movement (Eq. (3)) causes the
experiment results described above: some solids settle in the Solid
Collector, some scaled on reaction vessels, some was captured by
Condenser and some was carried out by efuents stream. According to Stokes Law (Eq. (1)), ut is proportional to the square of dp,
which suggests solid with smaller diameter was easier to be
brought to move upward by reaction medium (combining
Eqs. (1) and (3)). This can explain the average diameter is the biggest for Solid A, second for Solid B and the smallest for Solid C.

4. Conclusions and future work


A new SCWO system based on DGSWR has been designed and
described in detail. The preliminary experimental results indicate
the gas seal of DGSWR, which is the kernel of the new SCWO system, has been achieved under 2829 MPa and around 400 C.
Through the multi-feed injection technologies, sewage sludge with
a solid content up to 11.78% DS can be safely pumped and preheated, and mixed with high temperature water to form supercritical medium. The COD removal efciency can reach up to 99.15%.

This work was nancially supported by the 100-talent program


of Chinese Academia of Sciences (Y33Z050M10), the two Key Technology R&D Programs of Chongqing (Grant number: cstc2012ggsfgc20001 and cstc2011ggC20014), the National Natural Science
Foundation of China (Grant number: 41203047) and the Key Laboratory for Solid Waste Management and Environment Safety Open
Fund (Grant number: SWMES 2013-06).

References
[1] W. Wagner, A. Kruse, International Steam Tables Properties of Water and
Steam Based on the Industrial Formulation IAPWS-IF97, second ed., Springer,
Berlin, 2007. p. 5.
[2] M.D. Bermejo, M.J. Cocero, Supercritical water oxidation: a technical review,
AIChE J. 52 (2006) 39333951.
[3] V. Vadillo, J. Sanchez-Oneto, J.R. Portela, E.J. Martinez De La Ossa, Problems in
supercritical water oxidation process and proposed solutions, Ind. Eng. Chem.
Res. 52 (2013) 76177629.
[4] V. Vadillo, J. Snchez-Oneto, J.R. Portela, E.J. Martnez de la Ossa, Chapter 9
supercritical water oxidation for wastewater destruction with energy
recovery, in: V. Anikeev, M. Fan (Eds.), Supercritical Fluid Technology for
Energy and Environmental Applications, Elsevier, Boston, 2014, pp. 181190.
[5] P. Cabeza, J.P.S. Queiroz, S. Arca, C. Jimenez, A. Gutierrez, M.D. Bermejo, M.J.
Cocero, Sludge destruction by means of a hydrothermal ame. Optimization of
ammonia destruction conditions, Chem. Eng. J. 232 (2013) 19.
[6] P.A. Marrone, Supercritical water oxidation-current status of full-scale
commercial activity for waste destruction, J. Supercrit. Fluids 79 (2013) 283
288.
[7] P.A. Marrone, M. Hodes, K.A. Smith, J.W. Tester, Salt precipitation and scale
control in supercritical water oxidation Part B: Commercial/full-scale
applications, J. Supercrit. Fluids 29 (2004) 289312.
[8] P.A. Marrone, G.T. Hong, Corrosion control methods in supercritical water
oxidation and gasication processes, J. Supercrit. Fluids 51 (2009) 83103.
[9] P. Kritzer, E. Dinjus, An assessment of supercritical water oxidation (SCWO)
existing problems, possible solutions and new reactor concepts, Chem. Eng. J.
83 (2001) 207214.
[10] M. Hodes, P.A. Marrone, G.T. Hong, K.A. Smith, J.W. Tester, Salt precipitation
and scale control in supercritical water oxidation Part A: Fundamentals and
research, J. Supercrit. Fluids 29 (2004) 265288.
[11] Z. Chen, G. Wang, Z.A. Mirza, S. Yang, Y. Xu, Study of transpiring uid dynamics
in supercritical water oxidation using a transparent reactor, J. Supercrit. Fluids
88 (2014) 117125.
[12] S. Yang, G. Wang, Y. Xu, New design of supercritical water oxidation reactor for
sewage sludge treatment, Adv. Mater. Res. 774776 (2013) 212215.
[13] A. Martin, M.D. Bermejo, M.J. Cocero, Recent developments of supercritical
water oxidation: a patents review, Recent Pat. Chem. Eng. 4 (2011) 219230.
[14] D.H. Xu, S.Z. Wang, Y.M. Gong, Y. Guo, X.Y. Tang, H.H. Ma, A novel concept
reactor design for preventing salt deposition in supercritical water, Chem. Eng.
Res. Des. 88 (2010) 15151522.
[15] E.U. Franck, Dense uids new aspects and results, Phys. B C 139 (1986) 21
30.
[16] B. Wellig, Transpiring wall reactor for supercritical water oxidation (Doctoral
Thesis), No. 15038, ETH Zurich, Switzerland, 2003.
[17] B. Wellig, K. Lieball, P.R. von Rohr, Operating characteristics of a transpiringwall SCWO reactor with a hydrothermal ame as internal heat source, J.
Supercrit. Fluids 34 (2005) 3550.
[18] R.M. Serikawa, T. Usui, T. Nishimura, H. Sato, S. Hamada, H. Sekino,
Hydrothermal ames in supercritical water oxidation: investigation in a
pilot scale continuous reactor, Fuel 81 (2002) 11471159.
[19] P.R. Von Rohr, K. Prikopsky, T. Rothenuh, Flames in supercritical water and
their applications, Strojnicky Casopis 59 (2008) 91103.

Z. Chen et al. / Chemical Engineering Journal 269 (2015) 343351


[20] P. Cabeza, M. Dolores Bermejo, C. Jimenez, M. Jose Cocero, Experimental study
of the supercritical water oxidation of recalcitrant compounds under
hydrothermal ames using tubular reactors, Water Res. 45 (2011) 24852495.
[21] F. Zhang, C. Xu, Y. Zhang, S. Chen, G. Chen, C. Ma, Experimental study on the
operating characteristics of an inner preheating transpiring wall reactor for
supercritical water oxidation: temperature proles and product properties,
Energy 66 (2014) 577587.
[22] F. Cansell, Method for treating waste by hydrothermal oxidation, WO Patent
020414 (2002).
[23] S. Chkoundali, S. Alaya, J.-C. Launay, S. Gabsi, F. Cansell, Hydrothermal
oxidation of olive oil mill wastewater with multi-injection of oxygen:
simulation and experimental data, Environ. Eng. Sci. 25 (2008) 173179.
[24] S. Vielcazals, J. Mercadier, F. Marias, D. Mateos, M. Bottreau, F. Cansell, C.
Marraud, Modeling and simulation of hydrothermal oxidation of organic
compounds, AIChE J. 52 (2006) 818825.
[25] J. Portella, D. Mateos, F. Mancini, C. Marraud, F. Cansell, Hydrothermal
oxidation with multi-injection of oxygen: simulation and experimental data,
J. Supercrit. Fluids 40 (2007) 258262.
[26] V. Vadillo, M.B. Garcia-Jarana, J. Sanchez-Oneto, J.R. Portela, E.J. Martinez de la
Ossa, New feed system for water-insoluble organic and/or highly concentrated
wastewaters in the supercritical water oxidation process, J. Supercrit. Fluids 72
(2012) 263269.
[27] M. Schubert, J.W. Regler, F. Vogel, Continuous salt precipitation and separation
from supercritical water. Part 1: Type 1 salts, J. Supercrit. Fluids 52 (2010) 99
112.
[28] M. Schubert, J.W. Regler, F. Vogel, Continuous salt precipitation and separation
from supercritical water. Part 2. Type 2 salts and mixtures of two salts, J.
Supercrit. Fluids 52 (2010) 113124.
[29] K. Prikopsky, B. Wellig, P.R. von Rohr, SCWO of salt containing articial
wastewater using a transpiring-wall reactor: experimental results, J. Supercrit.
Fluids 40 (2007) 246257.

351

[30] M.D. Bermejo, F. Fdez-Polanco, M.J. Cocero, Effect of the transpiring wall on the
behavior of a supercritical water oxidation reactor: modeling and
experimental results, Ind. Eng. Chem. Res. 45 (2006) 34383446.
[31] E. Fauvel, C. Joussot-Dubien, V. Tanneur, S. Moussiere, P. Guichardon, G.
Charbit, F. Charbit, A porous reactor for supercritical water oxidation:
experimental results on salty compounds and corrosive solvents oxidation,
Ind. Eng. Chem. Res. 44 (2005) 89688971.
[32] J. Abelleira, J. Snchez-Oneto, J.R. Portela, E.J. Martnez de la Ossa, Kinetics of
supercritical water oxidation of isopropanol as an auxiliary fuel and co-fuel,
Fuel 111 (2013) 574583.
[33] F.J. Yin, Y.J. Xu, G.W. Wang, S. Yang, H.Z. Chen, Z. Chen, Macromolecular
products from bio-solids and its morphologic change employing hydrothermal
treatment, Adv. Mater. Res. 864867 (2014) 19761980.
[34] J.R. Portela, E. Nebot, E.M. de la Ossa, Kinetic comparison between subcritical
and supercritical water oxidation of phenol, Chem. Eng. J. 81 (2001)
287299.
[35] J. Sanchez-Oneto, F. Mancini, J.R. Portela, E. Nebot, F. Cansell, E.J. Martinez de la
Ossa, Kinetic model for oxygen concentration dependence in the supercritical
water oxidation of an industrial wastewater, Chem. Eng. J. 144 (2008) 361
367.
[36] M. Goto, T. Nada, A. Kodama, T. Hirose, Kinetic analysis for destruction of
municipal sewage sludge and alcohol distillery wastewater by supercritical
water oxidation, Ind. Eng. Chem. Res. 38 (1999) 18631865.
[37] Jiahua Zhu, Shichao Ye, Sulan Xia, Principles of Chemical Engineering, second
ed., Science Press of China, Beijing, 2005. pp. 206207.
[38] M. Dolores Bermejo, A. Martin, J.P.S. Qu-iroz, I. Bielsa, V. Rios, M. Jose Cocero,
Computational uid dynamics simulation of a transpiring wall reactor for
supercritical water oxidation, Chem. Eng. J. 158 (2010) 431440.
[39] NIST, Thermo physical properties of uid systems. Available from: <http://
webbook.nist.Gov/chemistry/uid/>.