Beruflich Dokumente
Kultur Dokumente
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
supercritical conditions.
Sewage sludge with 2.6211.78% DS
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.
344
345
Fig. 3. Picture of the Flange connecting Reaction Vessel 1 and Reaction Vessel 2.
346
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
19.73 0.12
45.53 0.10
28.05 0.13
4.77 0.11
4.57 0.01
0.80 0.06
61.81
241 2
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.
Table 2
Operation conditions.
Exp.
1
2
3
4
5
Air
Solid
content
(% DS)
Mass ow rate
(kg h1)
Isopropanol
concentration
(wt.%)
Mass ow rate
(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
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
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):
ut
dp qp qg
18l
dp up q
Rep
up u ut
Q =q
3600A
n
X
vi Y i
Fig. 9. Images of pressure bearing walls and porous walls after Exp. 5, without any
cleaning.
350
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.
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