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Hydrogen Gas Absorber Made of Manganese Dioxide
Hydrogen Gas Absorber Made of Manganese Dioxide
Hydrogen Gas Absorber Made of Manganese Dioxide
Akiya Kozawa*
Union Carbide Corporation, Battery Products Division, Cleveland, Ohio 44101
~
strong, p a r t i c u l a r l y i n the case of sheets. The solid
body is porous and most of the water added i n the
b l e n d i n g step is removed in the d r y i n g process.
The rate of h y d r o g e n absorption was tested with the
apparatus shown in Fig. 1 and 2 for fast adsorption and
slow absorption, respectively. The absorption is a H \
chemical reaction b e t w e e n H2 gas and MnO2. The ap-
paratus shown i n Fig. 1 is used to test the initial ab-
sorption rate employing a 1 ~-, 2g sample. The a p p a r a -
tus shown in Fig. 2 is used to m e a s u r e the total ab-
sorption capacity employing a 100-200 mg sample.
To operate the apparatus (Fig. 2) first the air i n the
test tube (B) was replaced b y N2 gas b y p u r g i n g while
the m o u t h of the test tube was m a i n t a i n e d slightly
above the oil level (H). T h e n .the oil level i n the test
tube was raised to a r o u n d (I) by applying a vacuum.
F i n a l l y H2 gas was introduced and the oil level was
b r o u g h t down to (H). All the fine plastic tubes (D)
were t h e n removed. The oil level was read from time
to time to m e a s u r e the h y d r o g e n gas u p t a k e b y the
sample. This was not a v e r y accurate m e a s u r e m e n t
(• cm3), b u t satisfactory for the present purpose.
* E l e c t r o c h e m i c a l S o c i e t y L i f e Member.
Key words: hydrogen, m a n g a n e s e dioxide, palladium, gas ab-
sorber.
c
Table I. Components of the hydrogen gas absorber
Typical
example Range
1193
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1194 J. Electrochem. Sot.: ELECTROCHEMICAL SCIENCE AND TECHNOLOGY August 1976
0.8 1.51 0.97 200 g.o • 0.5 3.0 -- 0.5 4.5 -- 0.5
2.0 1.47 0.95 195 23.0 IO.O 7.0
4.0 1.45 0.90 187 32.0 15.0 11.0
9.2 1,35 0.76 162 48,0 27.0 11.0
16.0 1.38 0.73 151 54.0 32.0 13.5
* T h e basic composition is as follows, the catalyst content being varied: MnO~: 160g, P d - c a r b o n : 0,4-16.8%, acetylene black: 2g, binder
( P o r t l a n d c e m e n t ) : 80g, steel wool: 5g.
dioxide influence the absorption rate as seen in Fig. 5 (polyethylene, polysulfone, etc.) sometimes deactivate
and 6. the catalyst, probably because the polymer covers the
Use of Hz gas permeable #lm.--If the hydrogen gas active centers of the palladium.
to be absorbed coexists with a solution, e.g., in the CO absorption.--It was found in a preliminary test of
alkaline manganese dioxide-zinc cell, this porous hy- this Pd-catalyzed hydrogen absorber for CO absorption
drogen absorber may be wrapped with a thin poly- that this material does have a relatively good capability
ethylene film through which I-I2 gas is permeable at a for CO adsorption.
sufficient rate but which prevents the solution from
going into the porous body. A 1 mil thick polyethylene
20
film (such as Zendel made by Union Carbide Corpora- I I I I
tion) has a sufficient hydrogen gas permeability for
most applications.
Other catalysts.--The catalyst can be platinum black
or other noble metals; palladium dispersed on carbon 15
o
is satisfactory and inexpensive compared to other noble
metal catalysts. The function of the palladium would
be the dissociation of hydrogen molecules to atomic 9
hydrogen. lO
Bonding agent.--Among various bonding agents in-
cluding organic plastics dissolved in organic solvents,
a few inorganic binders, water, glass, and cement
were found to be m o s t convenient. Organic plastics
c 0 I I I I I
0 1 2 3 4 5 6
Time, Days
Fig. 3. Hydrogen gas absorption by a 100 mg crushed sample
I having a formula shown in Table I,
t
I L
.
"////"
Z / I l l ,
I 5O I I I I
I : ;;S;,;,;,
D -
, i z / z z 5.5' ~ 4
40 - 4' --
I i
P~ I/
f7 AgO
Ag20
--
o
(H> _a
~ 20
7 ///
iii1~
..Q
rl//#
~ ....-. --"" ~ . . . . . . - - - 3
L,.. i
////.,
~ / / / / , , 2.2'
i / / /
o I ~ I J I ~'~
Fig. 2. Apparatus for measuring hydrogen gas absorption (see 0 1 2 3 4 5
text for operation). A: 10 cm3 beaker containing sample, B: an Time, hours
inverted test tube (3.5 cm in diameter, 30 cm long), C: hydrogen
gas, D: fine plastic tubes, E: hydrogen cylinder, F: nitrogen cylinder, Fig. 4. Hydrogen gas absorption by lg sample (MnO2 + Ag20 or
G: vaccum, H: oil level, I: top of the plastic rod, J: plastic rod, K: AGO). Ag20 or AgO content was as follows: 1.1':0.1%, 2.2':0.3%,
vacuum pump oil in 250 cm~ beaker. 3.3':1%, 4.4':3%, 5.5':10%.
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Vol. 123, No. 8 HYDROGEN GAS ABSORBER 1195
Acknowledgments
The a u t h o r wishes to t h a n k Mrs. H. M. J o s e p h for
h e r assistance in p r e p a r a t i o n of the manuscript.
~' 20 Manuscript s u b m i t t e d Jan. 29, 1976; revised m a n u -
script received March 10, 1976. This was P a p e r 2.19
p r e s e n t e d at the Chicago, Illinois, Meeting of t h e So-
ciety, May 13-18, 1973.
A n y discussion of this p a p e r will a p p e a r in a Discus-
sion Section to be p u b l i s h e d in the J u n e 1977 JOURNAL.
A l l discussions for the J u n e 1977 Discussion Section
o I I I I I should be s u b m i t t e d b y Feb. 1, 1977.
0 20 40 60 80 100 120
Time, Min. Publication costs of this article were assisted by
Union Carbide Corporation.
Fig. 6. Effect of particle size of manganese dioxide used in the
adsorber having a formula as follows: MnO2: 160g, Pd-catalyzed REFERENCES
carbon: 10g, acetylene black: 2g, cement: 40g, steel wool: 5g. 1. A. Kozawa, U. S. Pat. 3,893,870 (19'75) and 3,939,006
Particle size of MnO2: A: less than 40/~, B: 50-100#, C: 150-300~. (1976); Brit. Pat. 1,321,853 (1975); A u s t r i a n Pat.
302,436 (1972); Belgian Pat. 755,337 (1971); G e r -
m a n Pat. DT 2,042,266 (1971).
Mechanism of MnOz reduction.--The r e d u c t i o n of 2. C. S. Brooks, J. Catalysis, 4, 535 (1965).
MnO2 in d r y cells has been e x t e n s i v e l y studied (3-5). 3. A. K o z a w a and J. F. Yeager, This Journal, 112, 959
A c c o r d i n g to the studies, the electrochemical r e d u c t i o n (1965).
process is a p r o t o n injection into t h e MnO2 lattice at 4. A. K o z a w a and R. A. Powers, ibid., 113, 870 (1966).
least up to MnOl.~, as shown b e l o w 5. A. K o z a w a and R. A. Powers, J. Chem. Education,
49, 587 (1972).
MnO2 4- H20 -k e - --> MnOOH -p O H - 6. I n t e r n a t i o n a l common s a m p l e of m a n g a n e s e dioxide,
This Journal, 119, 152C (1972). The MnO2 samples
The reduction of MnO2 b y H2 gas w o u l d involve the a r e a v a i l a b l e from the I. C. S a m p l e Office, spon-
same mechanism, a l t h o u g h t h e source of protons is sored by the Cleveland Section of The Electro-
chemical Society, P. O. Box 6116, Cleveland, Ohio
H2 ( : 2H) i n s t e a d of H20 ( : H + -~- O H - ) . 44101.
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