Applied Thermal Engineering 100 (2016) 893–901

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Applied Thermal Engineering

j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / a p t h e r m e n g

Research Paper

Water vapor sorption performance of ACF-CaCl2 and silica gel-CaCl2

composite adsorbents
J.Y. Wang, R.Z. Wang *, L.W. Wang
Institute of Refrigeration and Cryogenic, Key Laboratory of Power Machinery and Engineering of MOE, Shanghai Jiao Tong University, Shanghai 200240,
China

H I G H L I G H T S

• A novel composite adsorbent for air-to-water system is proposed.

• The water uptake performance of ACF-CaCl2 is three times more than silica gel-CaCl2.
• SEM, ICP and ASAP2020 are adopted to analyze the micro characteristics of compounds.

A R T I C L E I N F O A B S T R A C T

Article history: A novel composite adsorbent of host matrix of CaCl2 was developed to increase mass transfer area and
Received 28 December 2015 enhance adsorption performance for air-to-water system under hot and humid conditions. The host matrix
Accepted 26 February 2016 is activated carbon fiber felts (ACF FELT) fabricated by viscose-based fibers. Scanning electron micro-
Available online 4 March 2016
scope (SEM) and Micromeritics ASAP2020 were adopted to observe the micro characteristics of matrix.
Inductive coupled plasma emission spectrometer (ICP) was used to test the quality of impregnation and
Keywords:
water crystallization carried by calcium chloride in synthesis. The preparation processes, pore struc-
Activated carbon fiber
tures, quantities of crystallization water of calcium chloride and impregnated salt, as well as the non-
Silica gel
Composite adsorbents equilibrium adsorption performances were studied, and the results were compared with the composite
Matrix structure adsorbents with SC matrix. Research shows that ACF is more suitable as the matrix of composite adsorbents,
Sorption performance and ACF30 has the best sorption performance of water uptake 1.7 g/g, which is three times more than
silica gel-CaCl2. Furthermore, ACF compound can be retested without rupture or carryover. Coefficient
of adsorption rate of water uptake was obtained using Linear Driving Force model.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction The selection of SWSs is a crucial for the air-to-water adsorp-

Fresh water source is essential to human beings and animals,
while its shortage in islands and arid regions threatens the surviv-
al of creatures and restricts human existing activities [1]. As the
classical methods to extract fresh water from environment, desal-
ination using traditional energy consumption mode had been
extensively studied [2]. However, most of existing apparatuses are
featured by high power consumption and production cost [3,4]. Con-
sequently, desalination is confined into seashore and offshore
environment. In contrast, the air-to-water facility adopting Selec-
tive Water Sorbents (SWSs) to extract fresh water from atmosphere
is more widely applicable in most regions. And it can be driven by
sustainable energy such as solar energy and waste heat, which
reduced energy consumption.
* Corresponding author. Tel.: +86 21 34206548; fax: +86 21 34206548.
E-mail address: rzwang@sjtu.edu.cn (R.Z. Wang).
tion system. The ideal material should possess excellent adsorption
performance and the ability to store the adsorbed water until it is
heated to desorb. Aristov et al. studied the sorption equilibrium of
the SWSs and designed a system to demonstrate the feasibility of
solar-driven fresh water production [5], however, the system was
proposed as a prototype and the water uptake performances of
adsorbents are unsatisfactory. Numerous novel porous media could
be used as SWSs to improve the performance of air-to-water system,
including nanoporous inorganic materials and polymer [6,7], such
as aluminophosphates [8], zeolites [9], metalloaluminophosphates,
aerogels [10], Metal Organic Framework (MOF) [11]. However, most
of the new materials are too expensive to be popularized or applied
to the system. Composite adsorbents, as an important part of SWSs,
received great attention for their economical, practical and stable
features. Composite adsorbents are generally composed of two parts:
chemical active salt and the matrix. Salt plays a major role of water
adsorption, and the matrix normally provides the container for the
inorganic salt. Thus water vapor is sufficiently adsorbed by inor-
ganic salt thanks to the channel capillary force. Silica gels [12,13],

http://dx.doi.org/10.1016/j.applthermaleng.2016.02.100
1359-4311/© 2016 Elsevier Ltd. All rights reserved.
894 J.Y. Wang et al./Applied Thermal Engineering 100 (2016) 893–901
ordered mesoporous silicate [14–17] and activated carbon [6] are
widely used host materials. Aristov et al. pioneered in fabricating
and developing composite adsorbents with the method of impreg-
nating hygroscopic salts (CaCl2, LiBr, LiNO3, etc.) [18,19] into the pore
cavities of host matrixes (silica gel, alumina, MCM-41) [20,21]. CaCl2
were wildly employed in compound adsorption material because
of its low cost, non-toxic, and remarkable water absorption perfor-
mance. Liu and Wang studied the effects of pore structure of silica
gel matrix and different ratios of CaCl2 solution on sorption prop-
erty of the composite adsorbents [22]. Daou et al. presented a series
of equilibrium adsorption isotherms of compound adsorbents with
CaCl2 and silica gel in various proportions at different tempera-
tures and humidity [23]. However, the composite adsorbents with
the host matrix of silica gel or ordered mesoporous silicate have
the fatal flaws of lyolysis [22] or carryover [24], rupture, and low
adsorption capacity per unit mass. Yu et al. explained that the re-
striction of pore volume was the real reason for carryover and the
effective way to address the problem was reducing the concentra-
tion of the solution [24], which would inevitably lead to degradation
of adsorption performance.
Adopting Active Carbon Felt (ACF) as the host matrix of the com-
posite adsorbents seems to be a promising way to substitute silica
gel. Hitherto, ACF is widely used for sewage treatment and solvent
recovery due to its huge surface area (1380 m2/g), excellent me-
chanical properties (internally non-breakable for fiber strength and
externally easy to be tailored), and fast intraparticle adsorption ki-
netics [25]. Thanh et al. studied the influence of ACF adsorption
principle in terms of pore size distribution (PSD) and pore wall struc-
ture [26]. Though ACF is an ideal host matrix for active salt, it was
found not suitable as pure adsorbent for its unsatisfactory adsorp-
tion strength. Nowadays composite adsorbents with ACF as matrix
were mainly used for ammonia refrigerant [27]. Dellero et al. com-
pared impregnated carbon fibers with MnCl2 (ICF) and graphite fibers
intercalation compounds with MnCl2 (GFIC) to produce composite
adsorbents, and ICF was adopted for easier preparation and the
similar result with GFIC [27]. Vasilievd et al. manufactured com-
posite adsorbents with the method of impregnating metal chloride
aqueous solution into ACF as matrix [28,29].
Fig. 1. Developing procedures of the composite adsorbents with ACF as matrix. (a) The ACF is dried in the oven, (b) impregnation, (c) the ACF is dried in the oven after
impregnation.
Fig. 2. Developing procedures of the composite adsorbents with silica gel as matrix. (a) The SC is dried in the oven, (b) impregnation, (c) standing for 48 hours. (d) The SC
is dried in the oven after impregnation.
In this study, CaCl2 was selected as water vapor sorbent [30], while
ACF and silica gel were selected and compared as the water absor-
bent matrix for air-to-water adsorption system.
2. Development of composite adsorbents
The ACF with the thickness of 1 mm and the silica gel with the
grain diameter of 2–4 mm were employed for composite adsorbents.
Firstly, the ACF felt was cut into 6 cm × 6 cm pieces and then dried
in an oven at the temperature of 120 °C for 4 hours so that water
and other impurities got out of pores sufficiently. Then the ACF felts
were sealed and cooled down to room temperature. The four pieces
of ACF felts were impregnated in the aqueous solution CaCl2 with
the mass concentration of 10%, 20%, 30%, 40% respectively at the
temperature of 20 °C for 8 hours, which abbreviated to ACF10, ACF20,
ACF30, ACF40. The schematic procedure was shown in Fig. 1 and
2 mm of the samples were immersed in the solution. Due to the
extremely strong capillary force of ACF felts, the liquid was ab-
sorbed from the bottom to the top of the samples, and the effective
impregnation length is 6 cm. The ACF material is anisotropic ac-
cording to the way of fiber weaving. In order to study the impact
of the direction of the fibers on impregnation, two pieces of ACF
felt impregnating in 30 wt% solution were developed. One fiber di-
rection of ACF was vertically to the solution level (ACFV), the other
parallel to the solution lever (ACFP). In order to reduce experimen-
tal error, three groups of samples were tested.
Meanwhile, the silica gel named type C with the average pore
diameter of 8–10 nm was also dried in the oven at the tempera-
ture of 120 °C for 4 hours. It was then sealed and cooled to room
temperature. After that the silica gel was immersed into calcium
chloride aqueous solution with different mass concentrations of 10%,
20%, 30%, and 40% at room temperature for 48 hours, which were
abbreviated to SC10, SC20, SC30, SC40 (Fig. 2). A vacuum suction
filter bottle connected with a vacuum pump was used to separate
the samples and the liquid, and remove the solution in the gaps and
on the surfaces of silica particles. Finally, the composite samples were
dried again in oven at 120 °C until no weight reduction can be ob-
served. The actual proportion of the CaCl2 in the composite adsorbent
 J.Y. Wang et al./Applied Thermal Engineering 100 (2016) 893–901 895

Table 1 0.89
Parameters of different composite adsorbents.
ACFP
Material Proportion of CaCl2 0.88 ACFV
ACF as the matrix ACF10 0.587 0.87
ACF20 0.622
ACF30 0.669 0.86

Ratio
ACF40 0.611
Silica gel as the matrix SC10 0.072 0.85
SC20 0.145
SC30 0.230 0.84
SC40 0.255
0.83

0.82
is shown in Table 1 and the accuracy of the electronic scales used 1 2 3
to weight the matrix and the composite adsorbents is 0.001 g. Sample rank

Fig. 4. Effect of fiber orientation on impregnation.

3. Experimental results

3.1. Features of adsorbents before and after impregnation

3.1.1. Adsorbents with the ACF as the matrix
Actually, before impregnation the ACF felt material is soft and
flexible. While it became stiffened after impregnation of the salt and
drying process. Fig. 3 shows the appearance of ACF, ACFV and ACFP.
Fig. 3a presents texture features of pure ACF, which is black and soft.
After impregnation in CaCl2 solution, i.e. ACFP and ACFV, the dry
samples turn to be white partially and hard inside, due to the salt
padding into fibers’ gap. However, ACFP and ACFV are different with
each other. (1) The salt level is approximately in agreement with
the direction of the fibers. In Fig. 3b, the white salt is vertical dis-
tribution, while in Fig. 3c, the salt presents horizon distribution. (2)
Salt decreases with height increasing gradually. Both ACFV and ACFP
are black at the top, and white at the bottom. This is a result of the
combined effect of fiber’s capillary forces and solution gravity, except
for the 2 mm bottom parts of the samples which were immersed
into solution.
In order to eliminate individual differences, three groups were
set to study the effects of the fiber direction on salt impregnation.
As Fig. 4 shows, three groups of samples were set to research the
effect of the fiber direction on salt impregnation, and the ratios of
salt were determined by:
Rc = ( Mc − Mhm ) Mc
The accuracy of the CaCl2 proportion is calculated based on the
equation as follows:
2 2
⎛ ∂R ⎞ ⎛ ∂R ⎞ as the concentration of the calcium chloride aqueous solution in-
Δηc = ⎜ Δn + Δn
⎝ ∂Mc ⎟⎠ ⎜⎝ ∂Mhm ⎟⎠
Take ACF10 for example, the error of the CaCl2 proportion is 0.012,
while the accuracy of electronic scales is 0.001.
The salt increased ratio of three specimens are close (in the vi-
cinity of 0.86), and the ratio of ACFP30 is slightly higher than ACFV30.
(a) (b) (c)
Fig. 3. (a) ACF before impregnation and after impregnation, (b) ACFV, (c) ACFP.
Thus in the following contents the ACFP is chosen if they are not
specifically mentioned.
Scanning electron microscope (SEM) was adopted to observe the
microscopic morphology of the samples. For ACF felts, it can be ob-
served in Fig. 5a that a large number of fibrils create a small quantity
of discontinuous texture grooves and wedge-shaped axial cracks at
macro level. One fiber consisted of a series of longitudinal fila-
ment fibers in irregular shape and different sizes in Fig. 5b, and the
rugged surface is very suitable for salt to adhere. The micro struc-
ture of ACF felts increases the surface area, enhances the capillary
force of the materials, and ensures it becomes a good carrier to
conduct and hold water.
After impregnation in 30% calcium chloride aqueous solution
(ACFV30), fiber surfaces are uniformly covered with calcium chlo-
ride as the solid sorbent for absorbing water vapor in the air, as
shown in Fig. 5c and d, and the space formed by the fibers can ac-
commodate a large number of liquid. The solid calcium chloride
absorbs water into a concentrated solution, which also has the strong
adsorption capacity of water. The calcium chloride attached to the
matrix composed of a large number of fibril, and the great capil-
lary force of the ACF felts ensures that plenty of fluids will not flow
out.
(1)
3.1.2. Adsorbents with the silica gel as the matrix
Fig. 6 showed the silica gel samples impregnated in different con-
centration of CaCl2 aqueous solution compared with the original Silica
gel. The color of dry sample turns from semi-transparent to white
(2)
creased from 9% to 30%. These concentrations were chosen instead
of 10%–40% to reduce carryover as far as possible at the high hu-
midity for 8 hours. The whiter silica gel indicated more calcium
chloride impregnating in them.
Additionally, the microstructure of composite samples with type
C silica gel as matrix is illustrated in Fig. 7. Silica gel grain is spher-
ical, and its surface is covered with white salt and shallow pits
(Fig. 7a). Meanwhile, the inorganic salt on surface can be clearly dis-
tinguished. Unfortunately the pore with 8–10 nm average diameter
cannot be discriminated under the condition of a magnification of
30,000 in Fig. 7b. Principally SEM utilizes an ultra-fine high-
energy electron beam for scanning on the sample, and inspires a
variety of physical information about it. Then surface morphology
of the sample is obtained with the devices, which accepts, en-
larges and displays this information. Due to the poor electric
conductivity of silica gel, it is unable to get higher magnification.
During the impregnation of the material and a series of
adsorption/desorption cycles, the silica gel ball structure is broken
widely in the four samples, which will increase simulation error and
896 J.Y. Wang et al./Applied Thermal Engineering 100 (2016) 893–901

(a) (b)

(c) (d)
Fig. 5. SEM pictures of ACF felt before and after impregnation; (a) 1500 times magnification of ACF, (b) 3000 times magnification of ACF, (c) 1500 times magnification of
ACF-CaCl2, (d) 12,000 times magnification of ACF-CaCl2.

uncertainty because simulation is based on spherical silica sor- transfer performance. On the other hand, the carryover problem will
bents. Meanwhile, the fragment will be more likely to drop out from occur, and once the salt solution overflowed from the matrix, the
the screen mesh, and it would inevitably lead to the mass de- mass decrease of the salt will result in the decay of the adsorption
crease of the silica gel, and consequently will impede the mass ability of the adsorbent.

Fig. 6. Silica gel samples impregnated in different concentration of CaCl2 aqueous solution: origin, 9%, 16%, 23%, 30%.

(a) (b)
Fig. 7. SEM pictures of type C silica gel after impregnation; (a) 82 times magnification of SC-CaCl2, (b) 30,000 times magnification of SC-CaCl2.
 J.Y. Wang et al./Applied Thermal Engineering 100 (2016) 893–901 897

(a) (b) (c)

Fig. 8. Different extent of carryover; (a) 80 min, (b) 130 min, (c) 210 min.

Another serious problem is the carryover of the silica gel com-
posite at high humidity and temperature. It occurs when the
concentration of salt solution is too high and the limited pore volume
cannot hold all the water adsorbed by the compound materials. Ac-
tually, the phenomenon of carryover depends on the concentration
or the pore volume as well as the operating condition and exper-
imental duration. Fig. 8 shows the phenomena of different extent
of carryover of SC30 under the condition of 30 °C and 70% relative-
ly humidity with different testing time. In Fig. 8, the silicone ball
transforms from white to transparent, which implies that the pore
is substantially filled with liquid, and it is not far from lyolysis. Once
the liquid drops out from the host matrix, the mass of the CaCl2 in
the composite adsorbents will decrease, thus the adsorption per-
formance was reduced.
of dry samples before and after the impregnation. However, such
method is not quite accurate for two main reasons. Firstly, CaCl2 will
adsorb water vapor from ambient air when it is exposed to atmo-
sphere; secondly CaCl2 inevitably contains crystal water, which can
only be dried out at temperature above 300 °C, where the silica gel
would burn down. In order to study the impregnation of CaCl2 in
detail, inductive coupled plasma emission spectrometer (ICP) is used
14
13
12
11
Adsorption Quantity (mmol/g)

10
3.1.3. Comparison of isothermal adsorption quantity 9
Micromeritics ASAP2020 gas adsorption analyzer is adopted to
8
measure the specific surface area using the conventional BET method,
7
and the porous characteristics of the composites using the BJH ACF
6 ACF 30
(Barret–Joyner–Halenda) method through standard nitrogen
adsorption/desorption measurement. The measurement of the sorp- 5
tion isotherms is implemented at 77 K, which is the temperature 4
of liquid nitrogen under atmosphere. The adsorption isotherms of 3
pure ACF and silica gel exhibit exactly two kinds of curves (Fig. 9a 2
and b), and it is mainly related to the differences of pore struc- 1
tures and sizes between silica gel and ACF. ACF belongs to micropore 0
medium with the pore diameter of 1.58 nm, which pertains to the 0.0 0.2 0.4 0.6 0.8 1.0
same order of magnitude as nitrogen molecule 0.304 nm. Thus the Relative Pressure (p/p0)
potential energy fields overlap and form a strong energy field to
attract other molecules, which enhances the interaction between
(a)
the solid surface and the molecules. Therefore, the adsorption iso-
therms of ACF rose sharply from the beginning, and became
saturated later because molecules filled the pore channel. For silica SC
30 SC16
gel, it belongs to the mesoporous materials with the average pore
Adsorption Quantity (mmol/g)

diameter of 7.14 nm, which is much greater than the diameter of SC 23

nitrogen molecules, so it presents a typical multi-molecular ad- SC 30
sorption. Fig. 9a shows nitrogen adsorption of dry ACF sample
increase quickly with relative pressure and saturated to 12.9 mmol/g 20
at p/p0 = 0.5, while curve of the ACF30 is smooth and the value is
small, 0.8 mmol/g at p/p0 = 0.5. For impregnated with calcium chlo-
ride sufficiently, the specific surface area of ACF is significantly
reduced. 10
The specific surface area of silica gel declines with the increas-
ing of the mass proportion of calcium chloride, and the certain
proportional relationship can be seen in Fig. 9b. The saturated values
of nitrogen adsorption of SC, SC16, SC23, SC30 are 32.5 mmol/g,
16.6 mmol/g, 13 mmol/g and 10 mmol/g respectively. 0
0.0 0.2 0.4 0.6 0.8 1.0
3.2. Research on the impregnation of CaCl2 Relative Pressure (p/p0)
(b )
3.2.1. Impregnation of CaCl2 measured by ICP
Generally, the quantity of CaCl2 remaining in the ACF felts and Fig. 9. Isotherms for nitrogen adsorption at 77 K; (a) adsorption quantity of ACF and
silica gel pores could be calculated by measuring the mass difference ACF 30, (b) adsorption quantity of SC, SC16, SC23 and SC30.
898
to measure the calcium chloride accurately. The mass of CaCl2 is cal-
culated by:
mol (CaCl2 )
MCaCl2 = MCa ×
mol (Ca )
Fig. 10 summarized the mass of immersed salt calculated by two
methods, electronic weighing scales and ICP. ACF-A and ACF-B are
the same material ACF. CaCl2 content of ACF-A is determined by elec-
tronic weighing scales, while CaCl2 content of ACF-B is determined
by ICP, Similarly for SC-A and SC-B. Fig. 10 shows that the results
of method A (electronic weighing scales) are higher than method
B (ICP). For example, the CaCl2 content is 0.33 at 0.2 concentration
in curve of SC-A, while value is 0.14 at the same concentration ac-
cording to the curve of SC-B. The difference is the quantity of
crystallization water carried by dry calcium chloride salt in sample.
Method B is a direct measurement of calcium, and thus it is more
accurate than method A.
The SC-B curve shows that the CaCl2 contents of SC are closely
related to the concentration of solution, and it increases with the
increase of the concentration of CaCl2 solution, but the growth rate
decreases at high concentration. The ACF-B curve shows that CaCl2
contents just fluctuate a little when solution concentration changes.
When the concentration is 0.4, the CaCl2 content is 0.61, which is
a little bit less than the value of 0.67 at the CaCl2 concentration of
0.3. The CaCl2 contents of ACF-B were six times higher than that
of SC-B at 0.1 concentration of CaCl2 solution, and two times higher
at 0.4 concentration of CaCl2 solution. In terms of salt impregna-
tion, performance of ACF is better than SC.
The impregnated salt existing in matrix (ACF or SC) was in the
form of crystalline hydrate. The difference between ACF-A and ACF-B
is the amount of water of crystallization, CaCl2 ⋅ nH2O, where n can
be obtained by
mACF SC− A − mACF SC−B
n=
mol (CaCl2 ) × MH2O
Table 2 shows the quantity of crystallization water for ACF and
SC. The values for the ACF are lower than that for SC which ben-
efits from the microstructure and the heat transfer capability of ACF.
Another advantage is that ACF materials can endure high temper-
ature for a long time without combustion, so ACF is applicable for
wider temperature range and provides larger water desorption
potential.
1.0
ACF-A
0.9
ACF-B
CaCl2 content in dry sample
SC-A
0.8
SC-B
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
0 5 10 15 20
the concentration of CaCl2 solution (%)
Fig. 10. Comparison of results between weighing method and ICP method.
J.Y. Wang et al./Applied Thermal Engineering 100 (2016) 893–901
Table 2
Water of crystallization in the impregnated salt.
Concentration 10% 20% 30% 40%
(3) Crystallizing water in ACF 1.69 1.98 1.97 2.91
composite adsorbent
Crystallizing water in SC 10.43 8.15 5.53 5.46
composite adsorbent
3.3. Adsorption performance
Eight adsorbents of ACFV30, ACFP30, SC30, SC23, SC16, SC9, SC,
SA (short for type A silica gel with 3–5 mm grain size and 2–3 nm
pore diameter) were tested in constant temperature and humidity
chamber. Electronic balance scales are adopted to measure the
weights of all the samples at different time points with accuracy
of 0.001 g. The weighing interval ranges gradually from 15, 20, 30,
60 to 80 minutes. Adsorption equilibrium was defined when the dif-
ference of the measured weights of two consecutive 80 minutes’
interval are less than 3%. The instrumental errors of the chamber
for the temperature and the relative humidity were ±0.5 °C and
±3%RH, respectively.
Rw = ( Meq − Mc ) Meq (5)
The accuracy of the water uptake is calculated based on the equa-
tion as follows:
2 2
⎛ ∂R ⎞ ⎛ ∂R ⎞ (6)
Δηw = ⎜ Δn + Δn
⎝ ∂Mc ⎟⎠ ⎜⎝ ∂Meq ⎟⎠
Take ACFP30 for example, the error of the water vapor is 0.008,
while the accuracy of electronic scales is 0.001.
Non-equilibrium adsorption properties are shown in Fig. 11. The
(4) ordinate represents the ratio of the increment of the sample mass
in different processes of experiments. The initial weight was ob-
tained from the sample dried under 120 °C for 4 hours. Both SA and
SC were set as the experimental comparison groups without CaCl2.
In Fig. 11a, at 500 min, the saturated quantity of water uptake of
ACFP30 was 1.6 g/g, nearly three times than performance of SC30
0.5 g/g, due to the notable increment of calcium chloride even though
both of them were impregnated in CaCl2 solution with the same con-
centration; Adsorption performance of SC30 was 5.5 times than SC
0.09 g/g and was two times higher than that of SA 0.25 g/g at
500 min. From Fig. 11b–d, it can be concluded that: (1) saturated
adsorption performance of ACFP30 was a little better than that of
ACFV30; (2) adsorption of ACFP30 was 3–4 times higher than that
of SC30, and was 6–7 times higher than that of SA, and was 17–18
times higher than that of SC; (3) the higher the concentration of
calcium chloride solution is, the greater the water uptake per unit
mass of adsorbents is. The reason for the high water uptake of ACF30
is the fibers woven micro-structure, and ACF has the huge surface
area and capillary force to adsorb and hold more salt liquid than
SC owning to this structure.
It is worth noting that SC30 composite adsorbents presented dif-
ferent levels of carryover problem under the experimental conditions
after 200 minutes. What was worse, after several cycles of adsorp-
tion and desorption, some parts of silica gel composite adsorbents
were ruptured, others seemed complete but got some cracks on the
surface.
3.4. Dynamic characteristics of composite adsorbents
25 30 35 40 45
Adsorption of CaCl 2 composite adsorbents contains both
physisorption and chemisorption. Chemisorption occurs at the be-
ginning of the water adsorption reaction as CaCl2 carries water
 J.Y. Wang et al./Applied Thermal Engineering 100 (2016) 893–901
Fig. 11. Non-equilibrium adsorption performances of different adsorbents under 70% relative humidity and the adsorption temperature of (a) 20 °C, (b) 25 °C, (c) 30 °C, (d)
35 °C.
molecules and gradually turns into CaCl2 ⋅ 6H2O , as a saturation state,
and then physisorption plays a leading role in the following ad-
sorption process. The time duration of chemisorption is much shorter
than that of physisorption, so the whole adsorption process can be
modeled as a physical adsorption.
The most popular model to study kinetics of physical adsorbents
is the linear driving force model (LDF). This model is based on an
assumption that the adsorption rate of a particle is direct propor-
tional to the difference between the inside and outside adsorbate
concentrations of adsorbent particles. Its original form of expres-
sion is
dx
= K ( xeq − x )
dt
After transformation and integration, Eq. (7) turns to:
x − x0
= 1 − exp ( − Kt )
xeq − x0
Since the materials had been heated in oven for 3 hours before
the experiments, water vapor and other impurities were substan-
tially removed. Therefore, x0 was taken as zero. Eq. (8) eventually
becomes:
x xeq = 1 − exp ( − Kt )
899
Fig. 12 shows the x xeq values of two compound materials varying
with time under the condition of 25 °C temperature and 70% rel-
ative humidity. The coefficient of adsorption rate K was figured out
by fitting the experimental curve. It can be seen that the K value
of SC30 is 1.48 × 10−4 which is a little bigger than 1.32 × 10−4 of ACF30
in terms of sorption kinetics. It means that adsorption rate of SC30
is a little faster than ACF30. The reason of this phenomenon is that
ACF has the huge capillary effect to hold the liquid and the salt block
some of the microporous channels after drying. However, the K
values of two composites are quite similar with each other and the
adsorption time is 8 hours, so it is not an obvious disadvantage for
ACF30.
(7)
4. Conclusions
ACF was adopted as the novel host matrix for CaCl2 as the SWS
for air-to-water system. Compared with SC, ACF seems to be a much
(8) better matrix for calcium chloride in aspect of adsorption proper-
ties, salt impregnation performance. The conclusions are listed as
follows:
(1) ACF30 is the optimum adsorbent for it has the best sorption
performance of water uptake under the test conditions, and
it was three times better than the performance of SC30. Fur-
(9) thermore, the problem of carryover does not occur for the
900 J.Y. Wang et al./Applied Thermal Engineering 100 (2016) 893–901

1.0 1.0
experimental data experimental data
calculate fitting data calculate fitting data
Dimensionless adsorbed quantity

Dimensionless adsorbed quantity

0.8 0.8

0.6 0.6
K=1.48×10-4
K=1.32×10-4
0.4 0.4

0.2 0.2

0.0 0.0
0 100 200 300 400 500 0 100 200 300 400 500
Time (min) Time (min)

(a) (b)
Fig. 12. Isothermal sorption kinetics of (a) ACF30 and (b) SC30 under 25 °C adsorption temperature and 70% relative humidity.

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