Novel zeolite adsorbents and their application for AHP and

Desiccant system

*Hiroyuki KAKIUCHI, Miki IWADE, Satomi SHIMOOKA,

Kazunori OOSHIMA, Masanori YAMAZAKI, Takahiko TAKEWAKI
Mitsubishi Chemical Group Science and Technology Research Center,
Toho-Cho 1, Yokkaichi, Mie, 510-8530, Japan, e-mail: 3803594@cc.m-kagaku.co.jp

KEY-WORDS
Zeolite, Adsorbent, Adsorption Heat Pump, Desiccant system, FAM

ABSTRACT

We have developed the novel water adsorbent material, named Functional Adsorbent
Material (FAM) that is aluminophosphate based zeolite with AFI or CHA structure, for AHP
or Desiccant air conditioning system. The water vapor adsorption isotherm of FAM is S-shape
and changed on temperature and has almost no (FAM-Z01) or very little (FAM-Z02)
hysteresis. FAM has very high durability against water vapor adsorption-desorption cycles.
This cycle test has reached 200,000 times (FAM-Z01) or 60,000 (FAM-Z02) so far. This
result shows that FAM has no problem for practical use. When the AHP is operated under the
condition in which TL/TM/TH = 283K/303K/333K, the adsorption capacity of FAM-Z01 is 4
times as much as A-type silica gel. On the assumption that AHP is operated under the
condition in which TL/TM/TH = 283K/313K/363K, the adsorption capacity of FAM-Z02 is 6
times as much as A-type silica gel. These results show that FAM brings about both the
compact AHP and the utilization of low temperature heats.

1. INTRODUCTION
For the purpose of global warming prevention, the heat obtained from co-generation
apparatus, fuel cells, cooling water for automobile engines, solar energy has strongly been
desired to effectively utilize. Adsorption Heat Pump (AHP) has been studied and developed to
effectively utilize low-temperature waste heat of 373K or lower, especially from 333K to
353K. Although the conventional AHP which uses silica gel as adsorbent has come into
practical use, it looks like not diffusing widely due to its large size or low COP. AHP is
thought a good system to use low-temperature waste heat of 373K or below, especially 353K,
more than the absorption heat pump. AHP is required to minimize its size and to increase
COP. To overcome the above mentioned subjects, the development of the novel adsorption
material which has big adsorption capacity in the operation range and the development of
excellent heat exchanger which has enough heat/mass transfer characteristic are indispensable.
Water-silica gel (Watanabe et al., 1993), water-zeolite (Mizota, 1999), water-activated
carbon (Kakiuchi et al., 2003), ethanol-activated carbon (Kumita et al., 2003) are known as
working pare of the adsorption material and the refrigerant of AHP. The authors examined
water as the refrigerant from the reason that its evaporation latent heat is big; water is safe
material and is inexpensive.
AHP operation range is fixed by three temperatures, low temperature TL, middle
temperature TM and high temperature TH. For example, when AHP is operated under
following conditions TL=283K, TM=313K, TH=363K, the operating range is fixed as
adsorption relative pressure φ1=0.17 and desorption relative pressure φ2=0.11. Silica gel
adsorbs-desorbs very small amount of water in this operating range. This is the reason why
conventional AHP becomes large. From this point, the promising adsorbent which adsorbs
and desorbs large amount of water in narrow operating range is strongly desired.
The authors perceived aluminophosphate zeolite and succeeded in the development of novel
water vapor adsorbent material, named Functional Adsorbent Material (FAM). The physical
properties, water vapor adsorption isotherm and the ability of FAM as AHP adsorbent
material were evaluated in this paper.

2. EXPERIMENTAL
We developed the novel adsorbent FAM-Z01 and FAM-Z02.
FAM-Z01 is an AFI type molecular sieve having one-dimensional structure with 0.73 nm
windows and its framework consists of AlO4, PO4 and FeO4 tetrahedrons, where Al and P
atoms are partially substituted by Fe atoms. FAM-Z01 was synthesized from iron-containing
aluminophosphate gels in the presence of organic amines under the hydrothermal condition.
FAM-Z02 is a CHA type molecular sieve having three-dimensional structure. The structure
has large ellipsoidal cages that are called the chabazite (CHA) cages. Small guest molecules,
such as water, can enter the cages through 0.38 nm windows. FAM-Z02 framework consists
of AlO4, PO4 and SiO4 tetrahedrons, where Al and P atoms are partially substituted by Si
atoms. FAM-Z02 was also synthesized from silicoaluminophosphate gels in the presence of
organic amines under the hydrothermal condition. Both samples were checked by XRD
measurements to be of high crystallinity.
We used FAU type aluminosilicate (Catalysts & Chemicals Industries Co., Ltd.), A-type
silica gel (FUJI SILYSIA CHEMICAL LTD.) and Coconuts shell activated carbon (Calgon
Mitsubishi Chemical Corporation) as conventional adsorbents.
Basic properties of FAM-Z01 and FAM-Z02 were evaluated. Specific heat was measured
with heat insulation type specific heat measurement apparatus (SH3000 of Shinku Riko Inc.).
Density was measured by Archimedes method. Heat conductivity was measured with the hot
wire type heat conductivity measurement apparatus (ARC-TC-1000 of Agne Gijutu Center
Inc.). The water vapor adsorption isotherms at the temperature range of 298K to 328K were
measured by the volumetric adsorption apparatus (BELSORP18 BEL Japan Inc.). And the
adsorption-desorption isotherms of the high temperature domain of 328K to 363K were
determined by the gravimetric adsorption apparatus equipped with the magnetic suspension
balance (RUBOTHERM). Prior to adsorption measurements, the sample was out gassed at
393K under a vacuum for 5h.
The durability studies of FAM- Table-1 Physical properties of FAM-Z01 and FAM-Z02
Z01 and FAM-Z02 were conducted Sample Name FAMZ01 FAMZ02
using the durability measurement Granule
Bulk density g/ml 0.6-0.7 0.6-0.7
apparatus (Mitsubishi Chemical Co., Particle size (typical) µm 100-2000 100-2000
Ltd.). The test samples were 0.113(303K) 0.117(303K)
Thermal conductivity W/mK
exposed to a water vapor for 0.123(343K) 0.128(363K)
adsorption and heated around 363K Differential heat of kJ/mol 56.0 58.3
adsorption(H2O,298K) kJ/g-H2O 3.11 3.24
for desorption. This adsorption- 0.805(303K) 0.822(303K)
desorption cycles were repeated and Specific heat J/g K
0.896(343K) 0.942(363K)
after several cycle times, such as 20
thousand, 60 thousand, 200 thousand, water vapor adsorption isotherms of the test samples
were measured and compared with the fresh ones.

3. RESULTS AND DISSCUSSION

3-1. BASIC PROPERTIES
Basic physical properties of FAM 0.4
are shown in Table 1. The particle size
of adsorbent for AHP is fixed

adsorption amount of water

0.3
according with heat exchanger

[kg-H2O/kg-Adsorbent]
dimension. The authors have
succeeded to granule it from 100 0.2
micron-meter to 2,000 micron-meter. FAM-Z01
We confirmed that particle has enough FAM-Z02

stiffness to use in AHP system. We 0.1 FAU alminosilicate

A-type silica gel
also have succeeded to make FAM Activated carbon

powder for Desiccant system. 0

3-2.WATERVAPOR 0 0.1 0.2 0.3 0.4 0.5 0.6
Relative pressure [-]
ADSORPTION ISOTHERM
Figure 1 shows water vapor Figure 1 Water vapor adsorption isotherm of
adsorption isotherm in 298K of FAM- FAM-Z01, FAM-Z02 and conventional
adsorbents
Z01 and FAM-Z02 with other
conventional adsorbents. From Figure 0.25
1, water vapor adsorption isotherms of
FAM-Z01 and FAM-Z02 are quite 0.2
different than other conventional
(g-H2O/g-Adsorbent)
Amount of Adsorbate

adsorbents. FAM doesn’t adsorb much

0.15
water vapor in low relative puressure
range, but FAM starts to adsorb water
0.1 25C ads
vapor drastically when relative 45C ads
pressure was slightly increased. Water 60C ads
vapor adsorption isotherm of FAM 0.05 60C des
75C ads
looks like S-shape. It’s understandable
75C des
that FAM adsorbs and desorbs much 0
amount of water vapor in very narrow 0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50
operating relative pressure range. Relative puressure [-]
Next, the authors measured water Figure 2 Water vapor adsorption isotherm
vapor adsorption isotherms of FAM- of FAM-Z01 in different
Z01 and FAM-Z02 in different 0.40
temperature. Figure 2 shows water
0.35
vapor adsorption isotherms of FAM-
Z01 in 298K, 318K, 333K and 348K. 0.30
(g-H2O/g-Adsorbent)
Amount of Adsorbate

It was found that adsorption character

0.25
of FAM-Z01 was changed depending
on temperature. Also, desorption 0.20
performance was evaluated in 333K 298K ads
0.15 323K ads
and 343K. FAM-Z01 doesn’t have 328K ads
large hysteresis. It was found that we 0.10
363K ads
could use adsorption isotherm for 0.05 363K des
AHP performance calculation. Figure
0.00
3 shows water vapor adsorption 0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50
isotherms of FAM-Z02 in 298K, Relative puressure [-]
318K, 328K and 363K. It was found
that adsorption character of FAM- Figure 3 Water vapor adsorption isotherm
of FAM-Z02 in different temperature
Z02 was changed depending on temperature. Also, desorption performance was evaluated in
363K. Because FAM-Z02 have slight hysterisys, we should use desorption plot to calculate
AHP performance using water vapor adsorption isotherm. This temperature dependency
character acts good performance in AHP application. We evaluate AHP ability of FAM-Z01
and FAM-Z02 later.

3-3. DURABILITY
0.25
0.35

0.2 0.3
(g-H2O/g-Adsorbent)
Amount of Adsorbate

0.25

(g-H2O/g-Adsorbent)
Amount of Adsorbate
0.15
0.2
0 times
0.1 30,000 times 0.15
60,000 times 0 times
150,000 times 0.1 20,000 times
0.05
200,000 times 60,000 times
0.05
0
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0
0.00 0.05 0.10 0.15 0.20 0.25 0.30
Relative puressure [-] Relative puressure [-]

Figure 4 Water vapor adsorption isotherms Figure 5 Water vapor adsorption

in 313K of FAM-Z01 after adsorption- isotherms in 298K of FAM-Z01 after
desorption cycles, such as 20000, 60000 and adsorption-desorption cycles, such as
200000 times. 20,000 and 60,000 times.

The durability of adsorbent is an essential factor on AHP or desiccant system. In general,

aluminophosphate molecular sieves such as AlPO-17 and AlPO-18 are unstable in water
vapor adsorption-desorption cycles. Therefore such aluminophosphates are inapplicable to
industrial applications. But FAM aluminophosphates are very stable in such conditions. This
is another strong advantage for AHP or desiccant applications.
The durability studies of FAM-Z01 and FAM-Z02 were conducted using the durability
measurement apparatus (Mitsubishi Chemical Co., Ltd.). The durability results of FAM-Z01
are shown in Figure 4 and the results of FAM-Z02 are shown in Figure 5. From Figure 4, it
was found that FAM-Z01 had tough durability against water vapor adsorption-desorption
cycles. There is no difference between fresh water vapor adsorption isotherm and 200,000
cycles aged one.
Figure.5 shows fresh water vapor adsorption isotherm, 20,000 cycles aged one and 60,000
cycles aged one. 20,000 cycles one and 60,000 cycles one looks almost same, but both curve
are slightly different from fresh one. The authors think this phenomenon as follows. FAM-
Z02 starts to change its surface hydrophilic at very first stage. After surface condition has
been in stable condition after adaptation to water vapor, there is no large difference between
20,000 aged cycles and 60,000 aged cycles. This durability evaluation is kept to operate up to
200,000 cycles.

3-4. APPLICABILITY OF FAM AS AHP ADSORBENT

Here, let us consider the use of FAM-Z01 as an adsorbent for an AHP by using low-
temperature heats of 333K obtained from fuel cells, solar energy and so on. When the AHP is
operated under the condition in which TL/TM/TH = 283K/303K/333K and the operating range
is fixed as φ1 = 0.29 and φ2 =
0.21, the equilibrium 0.2
adsorption capacity in the 0.18
operating range (∆Q) is 0.16

(g-H2O/g-Adsorbent)
Amount of Adsorbate
△Q(Silica gel)
compared between FAM-Z01 0.14 =0.04g/g
and A-type silica gel. ∆Q is the 0.12 △Q(FAM)
0.1 =0.16g/g
difference of the equilibrium
0.08
adsorption amounts at between
0.06
φ1 and φ2. Fig.6 shows the 0.04
water vapor adsorption 0.02
isotherm at 303K and 0
desorption isotherm at 333K 0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40
for FAM-Z01 and the Relative puressure [-]
adsorption isotherm at 298K FAM-Z01 303K ads FAM-Z01 333K des Silica gel 298K

for the silica gel. Because the φ1=0.29 φ2=0.21

isotherm for the silica gel is not

Figure 6 Adsorption ability of FAM-Z01 and
changed depending on Silica gel
temperatures, the isotherm in
298K can be used for 303K- 0.3
adsorption and 333K-desorption
isotherms. Fig.6 clear indicates 0.25
Absorbed Amount [kg/kg]

that ∆Q of FAM-Z01 is 0.16g/g 0.2

and this amount is 4 times as much △Q(FAM)
0.15 =0.19g/g
as A-type silica gel (0.04g/g).
On the other hand, FAM-Z02 is 0.1
suitable for the AHP by using a △Q(Silica gel)
0.05 =0.03g/g
little bit higher temperature waste
heats obtained by cooling water for 0
automobile engines, etc. Here, let 0 0.05 0.1 0.15 0.2 0.25 0.3
Relative pressure [-］
us consider the AHP in the
operating condition that TL/TM/TH FAM-Z02 313K ads FAM-Z02 363K des silica gel 298K ads
φ1=0.17 φ2=0.11
= 283K/313K/363K and the
operating range is fixed as φ1 =
Figure7 Adsorption ability of FAM-Z02 and Silica gel
0.17 and φ2 = 0.11. Fig.7 shows
the water vapor adsorption isotherm at 313K and desorption isotherm at 363K for FAM-Z02
and the adsorption isotherm at 298K for A-type silica gel for comparison. ∆Q of FAM-Z02 is
0.19g/g and ∆Q of the silica gel is only 0.03g/g. That is, this amount of ∆Q is more than 6
times much than A-type silica gel.
When using FAM as adsorbents for AHP, the equilibrium adsorption capacity (∆Q) is 4-6
times as much as A-type silica gel. In other words, FAM is able to bring about one-fourth or
one –sixth downsizing of AHP compared with conventional ones.
These results show that FAM leads to both the compact AHP and the utilization of low
temperature heats, and implicate that the application of the AHP with FAM is spread out even
into a region that conventional AHP is inapplicable to.
Desiccant system is also required to minimize its size and utilize low temperature waste
heats. Therefore, FAM is a promising adsorbent to resolve such issues.

4. CONCLUSION
 We have developed the novel water adsorbent material, named Functional Adsorbent
Material (FAM) that is aluminophosphate based zeolite with AFI or CHA structure, for AHP
or desiccant air conditioning system.
The summary of FAM adsorption property is as follows;
1. The water vapor adsorption isotherm of FAM is S-shape and changed on temperature and
has almost no (FAM-Z01) or very little (FAM-Z02) hysteresis. Such unique properties
result in high adsorption capacity in a very narrow operating relative pressure range.
2. FAM has very high durability against water vapor adsorption-desorption cycles. This cycle
test has reached 200,000 times (FAM-Z01) or 60,000 (FAM-Z02) so far. This result shows
that FAM has no problem for practical use.
3. When the AHP is operated under the condition in which TL/TM/TH = 283K/303K/333K, the
adsorption capacity of FAM-Z01 is 4 times as much as A-type silica gel. On the
assumption that AHP is operated under the condition in which TL/TM/TH =
283K/313K/363K, the adsorption capacity of FAM-Z02 is 6 times as much as A-type silica
gel. These results show that FAM brings about both the compact AHP and the utilization of
low temperature heats.

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