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College of Resources and Environment, Graduate University of Chinese Academy of Sciences, Beijing 100049,
China
Earth College, Graduate University of Chinese Academy of Sciences, Beijing 100049, China
Abstract This study presents the first demonstration project in China for treatment of coal-bed methane (CBM)
co-produced water and recycling. The work aims to provide a research and innovation base for solving the pollution
problem of CBM extraction water. The reverse osmosis (RO) unit is applied to the treatment of CBM co-produced
water. The results indicate that system operation is stable, the removal efficiency of the total dissolved solids (TDS)
is as high as 97.98%, and Fe, Mn, and F are almost completely removed. There is no suspended solids (SS) detected in the treated water. Furthermore, a model for the RO membrane separation process is developed to describe
the quantitative relationship between key physical quantitiesmembrane length, flow velocity, salt concentration,
driving pressure and water recovery rate, and the water recovery restriction equation based on mass balance is developed. This model provides a theoretical support for the RO system design and optimization. The TDS in the
CBM co-produced water are removed to meet the drinking water standards and groundwater quality standards
of China and can be used as drinking water, irrigation water, and livestock watering. In addition, the cost for treatment of CBM co-produced water is assessed, and the RO technology is an efficient and cost-effective treatment
method to remove pollutants.
Keywords coal-bed methane co-produced water, high salt, pretreatment process, mass balance, reverse osmosis
INTRODUCTION
and cost-effective technologies are needed for the water to be used for beneficial purposes, such as irrigation, livestock or wildlife watering and habitats, and
various industrial uses [57].
Typically, technologies for treatment of highsalinity water include evaporation, ion exchange, electrodialysis and reverse osmosis [7]. The evaporation
method, which is mainly used for seawater desalination, requires massive heat; also, high salinity water
will cause fouling on the heat exchanger surface [7].
The dissolved salts or minerals can be removed by
ion-exchanger, but the pre- and post-treatment are required for high efficiency and the operation of regeneration of resin is complicated [7]. Dallbauman and
Sirivedhin employed electrodialysis for treatment of
high salinity water co-produced in oil-gas fields, obtaining a TDS removal efficiency of 93.4%96.5%
with a voltage 6.5 V and time of 60 min [8]. However,
the membrane module needs frequent cleaning and
fluctuations in water quality have a great impact on
the effectiveness of the electrodialysis method. High
pressure reverse osmosis (RO) processes have been
the technology of choice for high-salinity water desalination in the US and many other countries [9, 10].
The market share of RO desalination was 43% in 2004
and is forecasted to increase up to 61% in 2015 [11].
The advantages of RO include low energy requirements, low operating temperature, small footprint,
modular design, and low water production costs. Reverse osmosis with high desalination efficiency, for
303
304
which water quality fluctuations have no negative effect on the treatment effectiveness, is a feasible technology for high-salinity water treatment [1214].
The CBM co-produced water in Liulin County of
Luliang City, Shanxi Province, China, is high-salinity
water. In this work, a system with sand filtration (pretreatment) + ultrafiltration (pretreatment) + RO is employed for treatment of CBM production water in Liulin.
The effects of treatment process, the system performance and the reuse feasibility are examined according
to the output water quality and treatment cost.
Many mass transfer models have been developed
for the flux of salt and water through RO membranes
[1519]. Song et al. [16, 17] put forward the conception
of thermodynamic equilibrium that restricts the recovery of membrane and provided an alternative way for
optimization of membrane design and operation conditions. In this work, based on mass balance principle,
mass transfer equations for water and salt are derived,
and a model depicting the relationship between salt
retention, TDS concentration and water recovery is
obtained. The water recovery restriction equation is
developed based on mass balance. Furthermore, different operation ways of RO process are discussed and
appropiate operating conditions are determined according to the theoretical model.
2
2.1
PILOT-SCALE EXPERIMENTAL
Process
The feed water was CBM field co-produced water from Liulin County of Luliang City, Shanxi Province. A process with sand filtration + UF + RO was
utilized for treatment of the water with the capacity of
100 m3d1. First, the raw water was aerated to increase
dissolved oxygen in water, and then passed through a
manganese sand filter, sand filter and bag filter to remove Fe, Mn and suspended solids (SS). The water
passed the UF system and then went through a security filter into the RO system. Finally, the output water
from RO entered storage tanks. The process flowsheet
is shown in Fig. 1, and Fig. 2 shows an on-site picture
of the pilot-scale demonstration unit built in this work.
2.2
Treatment units
2.2.1 Pretreatment
(1) Manganese sand filter
Raw water entered the manganese sand filter
through the jet aeration. The manganese sand filter
consists of a filter plate, with the upper plate filled
with 12 mm manganese sand particles, which remove most of the SS, colloids, Fe, Mn and other impurities, and reduces turbidity.
(2) Sand filter
The sand filter is in form of a filter plate. Quartz
sands of 0.51 mm and 12 mm in diameter are loaded
from top to bottom within the sand filter, with a filtering accuracy of under 20 m. The sand filter mainly
removes SS and colloids to further reduce turbidity
and ensure that the turbidity of the output water is less
than 3 NTU.
(3) UF system
An X50 polypropylene hollow fiber ultra-filtration
membrane is used in the UF system, with a molecular
weight cutoff (MWCO) in the range of 80000100000
(membrane pore size of 0.10.25 m), the treated water turbidity less than 0.3 NTU and silting density index (SDI) less than 4. The system has six sets of
membranes arranged in parallel with a single membrane flux of 24 m3h1 and area of 105 m2. The concentrated water from UF is totally recirculated.
2.2.2 RO system
The spiral wound RO membrane is a composite
polyamide membrane (BW30-400) with a desalination
rate higher than 99.5% for a single membrane, which
is 1.016 m long and 0.1016 m in diameter. The height
of membrane channel is 1103 m and membrane resistance is 81010 Pasm1. The RO unit is operated at
the pressure around 1.8 MPa. The RO membrane system consists of three membrane modules, with three
membrane components arranged in series for each
membrane module. Membrane modules are in a 21
arrangement. The first treatment stage is composed of
two membrane modules and the concentrated water
produced by the first stage enters a second stage with
a single membrane module. Concentrated water is generated in the second stage, while pure water generated
in the first and second phases enters a storage tank.
2.3
The analysis of water quality is based on the Drinking Water Standard Test Methods (GB/T5750-2006),
Underground Water Standards (GB/T14848-1993)
and Drinking Water Standards (GB 5749-2006).
3 MODEL FOR RO SYSTEM BALANCE
EQUATIONS FOR CHEMICAL COMPONENTS
Figure 2
305
Figure 3
du ( x )
dc( x) c( x)v( x)(1 r )
u ( x)
0 (5)
H
dx
dx
Substituting Eq. (3) into Eq. (4) and integrating, we
have
c( x) 1
x rv ( x )
(6)
c0 c( x)dc( x) 0 Hu ( x) dx
c( x)
Substituting v( x) Hdu ( x) / dx into Eq. (6) and integrating, a concise relationship between c(x) and u(x)
is obtained
r
c( x)
u0
u ( x) c0
(7)
c r
(9)
R 1 0
c
This simple equation based on the mass balance
principle is applicable for various membranes. This
306
1
HRm
r
12 P k x
u
2 0 u ( x)dx f 0 c0 'p0
u ( x)
H
(13)
Dividing the membrane channel into n segments
of equal intervals 'x, if the interval is small enough,
Eq. (13) for every interval can be transformed to
Table 1
Well
pH
dui ( x)
dx
1
HRm
r
12P k
ui 0
'
u
x
f
ci 0 'p0
2 i0
ui ( x)
H
(14)
where subscript i indicates segment i. Integration of
Eq. (14) gives u(x). The Runge-Kutta-Fehlberg method
(denoted RKF45) is employed to solve the differential
equation with three initial values, ui0, ci0 and p0.
4
Process performance
CODMn
/mgL1
TDS
/mgL1
K+
/mgL1
Na+
/mgL1
Ca2+
/mgL1
Mg2+
/mgL1
NO3
1
/mgL
SO24
CO32
HCO3
F
/mgL1
Cl
/mgL1
/mgL
/mgL
/mgL1
1
1
1#
7.78
2.1
5466
7.4
1852.2
20.1
26.7
1.4
2.5
1973.2
143.3
N.D.
1797.5
7.62
2.9
4782
7.7
1698.4
20.4
24.2
1.2
1.3
1984.8
149.5
N.D.
1454.4
3#
7.49
2.6
4650
6.9
1681.2
19.8
31.1
1.4
1.5
1917.8
141.9
N.D.
1454.4
4#
8.40
0.5
1613
5.8
583.5
8.7
4.2
0.2
10.3
326.1
28.4
23.86
1058.2
5#
7.91
3.6
1620
13.4
602.0
12.6
4.6
0.4
8.8
330.0
27.0
N.D.
1121.4
307
Table 2
Water quality
Raw
water
RO
Manganese sand
Multi-medium
Removal
/%
UF
Output
Removal/%
Output
Removal/%
Output
Removal/%
Output
Removal/%
turbidity/NTU
409
12.4
96.97
1.4
88.71
<0.5
>64.29
<0.5
100
pH
8.64
8.39
8.03
8.33
8.33
6.46
5.01
22.45
5.01
3.51
29.94
1.19
66.10
81.58
5466
4180
3.01
5302
2.02
5196
0.75
105
97.98
98.08
1.58
1.51
4.43
0.90
40.40
0.85
5.56
0.23
72.94
85.44
1910
1200
37.17
1160
3.33
1100
5.17
57.4
94.78
96.99
0.22
N.D.
100
N.D.
N.D.
N.D.
100
0.04
N.D.
100
N.D.
N.D.
N.D.
100
2.25
1.40
37.78
1.45
1.71
N.D.
100
100
1
CODMn/mgL
1
TDS/mgL
1
NH3-N/mgL
1
Cl /mgL
1
Fe/mgL
1
Mn/mgL
1
F /mgL
RO model simulations
308
309
Figure 9 The dependency of water recovery rate on driving pressure in two stage treatment process (u0 0.18 ms1,
c0 5196 mgL1, L 6 m, Rm 81010 Pasm1)
predicted value;experimental value
system output water meets the Drinking Water Standards (GB 5749-2006), so it can be used as domestic
water as well as those for local road cleaning, watering plants, etc., in order to be fully utilized.
Table 3 compares the experimental results with
water quality standards. Most of the indicators for the
treated water meet the national first class standard for
underground water, except for chloride and ammonianitrogen. The concentration of chlorine compounds is
slightly higher than the national first class standard,
and the level of ammonia-nitrogen is slightly higher
than the national third class standard, but still meets
the drinking water standards. Thus CBM co-produced
water can meet domestic drinking water standards
after the water treatment process.
Table 3
fouling, and the water recovery rate will decrease accordingly. However, as shown in Fig. 10, the recovery
is unchanged with the increase of resistance until a
certain value is reached, which indicates that the recovery is independent of resistance during the initial
period of membrane fouling. The reason for this result
is the high driving pressure. Fig. 9 shows that the recovery increases little when the pressure exceeds 1.8
MPa. For the driving pressure of 2.0 MPa, these excessive pressures can compensate for the increase of
membrane resistance caused by membrane fouling, so
the recovery can maintain a certain level until the
membrane fouling is severe. The simulation results
suggest that a high system driving pressure will result
in bad membrane fouling that can not be detected earlier. For avoiding severe membrane fouling, the pressure of 1.8 MPa is appropriate from Fig. 9. Based on
the discussion, the RO process will be high efficient
and durable at 1.8 MPa pressure and 6 m membrane
length, with 70% water recovery under the condition.
Items
chroma
15
1
<0.5
6.58.5
8.33
N.D.
visible material
N.D.
1
SS/mgL
N.D.
total hardness/mgL1
550
150
N.D.
1.2
TDS/mgL
1000
300
105
Cl/mgL1
250
50
57.4
NO 2 /mgL1
0.001
N.D.
SO24 /mgL1
250
50
0.3
CODMn/mgL1
1
3
1
NO /mgL
10
0.6
NH3-N/mgL1
0.5
0.02
0.2
100
100
44
Fe/mgL1
0.5
0.1
N.D.
Mn/mgL1
0.3
0.05
N.D.
F/mgL1
1.0
N.D.
0.005
0.005
N.D.
Hg/mgL
0.001
0.00005
N.D.
Cd/mgL1
0.005
0.001
N.D.
As/mgL
0.01
0.005
N.D.
Zn/mgL1
1.0
0.05
N.D.
1
6+
Cr /mgL
1
1
1
0.3
N.D.
3.0
N.D.
4.4
4.5
Under the operating condition of 1.8 MPa pressure and 6 m membrane length the quality of the RO
<5
6.58.5
turbidity/NTU
pH
1
310
Table 4
Electricity bills
total installed power
30.00 kW
used power
14.00 kW
0.51 CNYkW1h1
8.00 h
57.12 CNYd1
reducing agent
flocculating agents
inhibitor
chemical costs
19.80 CNYd1
Labor costs
operator
labor costs
30.00 CNYd1
6.50 CNYd1
depreciation costs
45.00 CNYd1
maintenance costs
40.00 CNYd1
total
73.50 CNYd1
70.00 m3d1
180.42 CNYd1
2.58 CNYm3
costs, pharmacy, labor costs and replacement and depreciation charges. The water treatment capacity is 100
m3d1 and the output water is 70 m3d1. The treatment
cost for one ton of output water is assessed to be 2.58
CNY. A promising future for civilian use of CBM
co-produced water can be expected from the Table 4.
5
CONCLUSIONS
CBM fields produce large amount of high salinity water, which can feasibly be treated on a largescale using an RO system. The pilot-scale test results
indicate that the RO system runs smoothly and has a
good treatment effect for CBM co-produced water.
With a model for the RO membrane separation
process developed, the predicted values are in good
agreement with experimental values. This model provides a theoretical support for the RO system design
and operation condition optimization.
Through the pretreatment and RO system, turbidity,
Mn, Fe and F almost were almost completely removed.
CODMn removal efficiency was 81.6%, while 85.4%
for NH3-N, 97.0% for Cl and 97.6% for TDS. After
the treatment, the output water meets the Drinking
Water Standards (GB 5749-2006) in China, so it can
be used for domestic water and thus be fully utilized.
NOMENCLATURE
c
H
k
L
'p
R
Rm
r
t
u
v
K
'S
UH O
2
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