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Metal hydride compressor and its application in cryogenic technology
Journal o|
A~OYS AHD COMPOUHDS ELSEVIER
Journal of Alloys and Compounds 231 (1995) 907-909
Metal hydride compressor and its application in cryogenic technology Zhan Feng a, F|ao Deyou a, Jiang Lijun a, Zhang Liang b, Yu Xiaoyu b, Zhou Yiming b ~General Research ]nstitutefor Nonferrous Metals, 2 Xin Jie Kou Wai Street, Beijing 100088, People's Republic of China bCryogenic Laboratory, Chinese Academy of Sciences, Zhong guan cun, Beijing 100080, People's Republic of China
Abstract
The AB 2 and AB 5 type,; of hydrogen storage alloy have been investigated for meeting the requirements of making a metal hydride compressor with some characteristics applied in the cryogenic technology. Using this compressor, a cooling capacity of 0.4 W at 25 K was obtained with a Joule-Thomson microcooler, and 1.35 W at 77 K with a small G-M cooler was also tested. Keywords: Metal hydrides; Hydrogen compressor; Cryogenics;Liquid hydrogen;Joule-Thomson effect
1. Introduction The metal hydride ]hydrogen storage alloy is a functional material which can realize an energy transformation process to form a sorption compressor with the advantages of no moving parts, little vibration, without noise, long cycling life and use of low grade heat as the power, A sorption compressor has been developed and tested. A cooling capacity of 0.4 W at 25 K was obtained with a Joule-Thompson (J-T) loop, precooled by liquid nitrogen, which is suitable for application in aerospace, IR and space surveillance etc. [1-5]. This compressor was also coupled with a small G - M refrigerator running at 7 7 K with 1.35W cooling power, which is useful for superconductor research, electronic apparatus and cryosurgery equipment [6].
2. E x p e r i m e n t s
2.1. Properties o f hydrogen storage alloy for the compressor
developed an AB 2 type of titanium series Laves phase alloys such as Ti0.77Zr0.23(MnCrCu)z (alloy 1) and Ti0.85Zr0.15(MnCrV)2 and also an AB 5 type of LaNi 5 alloy. Fig. 1 shows the P - C - T curve of alloy 1 and Fig. 2 shows the van't Hoff curve for these three alloys. The test results of the single compressor is s h o w n in Table 1 for Ti0.77Zr0.~3(MnCrCu)2 alloy and in Table 2 for LaNi 5 alloy. The equilibrium pressure for the absorption of hydrogen at room temperature for these three alloys is 0.1-0.6 MPa, and the desorption equilibrium hydrogen pressure at 90-100°C is about 1.5-4.0 MPa. l0
"~n
;
O.
"
' x" 0.1 -
• 6 0 C desorption
As a hydrogen storage alloy used in a sorption compressor, besides having a good plateau property, lower hysteresis, easy activation, longer cycling life
zx 40 c obsorption • 4o c desorption 7 3 0 C obsorption x 3 0 C desorption
etc., it must possess a higher capacity of absorption
and desorption, good kJinetic properties in order to obtain a high hydrogen flow rate, suitable pressure difference and high pressure ratio at operating ternperatures. On the basis of these requirements, w e 0925-8388/95/$09.50 © 1995 Elsevier Science S.A. All rights reserved SSD1 0925-8388(95)01781-X
0 6 0 C absorptio
°°10
I
I
I
I
I
I
I
I
I
0.1 0.20.3 0.4 0.5 0.6 0.7 0.8 0.9 H/M Fig. 1. P-C-T curve for alloy 1.
I
I
.I
Z. Feng et al. / Journal of Alloys and Compounds 231 (1995) 907-909
908 10
pressors, three inlets, three auto-outlet valves and 12 solenoid valves controlled by a microcomputer, could supply a continuous hydrogen steam at a high pressure and suck in hydrogen at a low pressure when it circulated back from a J - T refrigerator or a G - M
o "l-i0.83Zr0A5(MnCrV)2 • TiO,77ZrO.23(MnCrCu)2 Iq LaNI5
z~
I
O. I 2.7
I 2.8
I 2.9
I I 3 3.1 1000/T(K)
I 3.2
I 3.3
Fig. 2. The van't Hoff curves for the three alloys, Table 1
The test results of the single compressor with Tio.77Zro23(MnCrCu)z alloy, Absorption conditions
cooler Every single compressor set is filled in with 0.8 Kg of alloy using a special packing m e t h o d in order to improve the thermal conductivity in the sorption bed. The thickness of this bed is 5 mm. T h e hot water at about 95 °C and the running water at r o o m temperature, used as heating and cooling media respectively, pass through both sides of the annular bed to enhance the heat transfer between the compressor and the water. The three compressors are installed in the compressor system with self-sealing fittings. The hydride compressor system includes six parts: metal hydride compressor sets, hydrogen source, fluid cycling loop, water circulation system, microcomputer control system and m e a s u r e m e n t system.
Desorption properties
P (MPa)
T (°C)
t emax T (min) ( M P a ) (°C)
Q" (1)
V (ml g ~min t)
0.3 0.3 0.4 0.6 0.6
18 8 7 18 8
3 3 3 3 3
33 74 96 59 90
11.1 24.9 32.3 19.9 30.3
2.2 2.7 3.4 4.2 4.5
90 97 99 99 92
a Total desorption amounts of hydrogen for 1 cycle, The absorption capacity at low temperatures and low pressures is 25-40 ml g min -1. It could require a metal hydride compressor with a hydrogen flow rate of 201min -1 and refrigeration t e m p e r a t u r e of 25 K.
2.2. Hydride compressor system The equilibrium pressures of the hydrogen storage alloy, which reacts with hydrogen at different temperatures, are different. After repeated reciprocal heating and cooling, the hydrogen storage material can realize the compressor function of absorption at low pressures (inlet) and desorption at high pressures (outlet). The h y d r i d e - h y d r o g e n compressor system is shown in fig. 3. This system, formed with three single com-
2.3. Application in the 25 K liquid-hydrogen temperature cryogenic technology The metal hydride compressor filled with the LaNi 5 alloy was coupled to a J - T cooler pre-cooled by liquid nitrogen. The cooling capacity of 0.4 W was measured after 95 min in closed cycling, when the inlet pressure is 1.4 MPa, the outlet pressure is 0.3 M P a and the flow rate is 201 min -1. Fig. 4 shows the decrease in temperature with time.
2.4. A application in the 7 7 K G - M refrigerator T o obtain liquid-nitrogen t e m p e r a t u r e from r o o m t e m p e r a t u r e with this compressor system, a G - M refrigerator was developed. A refrigeration power of 1.35 W at 77 K is obtained in an open-loop test when the inlet pressure is 2.0 MPa, and the outlet pressure is 0.6 MPa. It can be used in the m e a s u r e m e n t of the critical t e m p e r a t u r e of a superconductor with the benefits of realizing continuous m e a s u r e m e n t of the electrical properties of it was high accuracy, easy operation and quick measurement.
Table 2 The test results of the single compressor with LaNisalloy. Compressor
1 2 3
Absorption conditions
Desorption properties
P (MPa)
T (°C)
t
Pmax
(min)
(MPa)
T (°C)
Qa (1)
V (mlg t min ~)
0.3 0.3 0.3
15.5 14.5 15.5
3 3 3
2.6 2.4 2.4
97.5 95 93
80 75 94
30.7 28 35.6
a Total desorption amounts of hydrogen for 1 cycle.
Z. Feng et al. / Journal of Alloys and Compounds 231 (1995) 907-909
GH2 supplyvolve [
J Hot water JI Coolwaterin I t~re'erv°ir Check valve ,- ...... ~SvOo;y ~ ~jl~~
Low pressure
hadingtank
r, ,eo e
909
l
valve
Hiolghing ts::~e
C°°~utater
Fig. 3. The metal hydride compressor system.
w5o v ~-
Liquirange dhydrogen
I00
~,
~ Ir~ ~
50
20o
25
~ Time(min)
50
75
~O 0
,~
Fig. 4. J - T cryogenic temperature lowering curve.
3. Conclusions
(1) AB2-type
Ti~.vTZro.23(MnCrCu)z
and
Ti0.85Zr0.15(MnCrV)2 and ABs-type LaNi 5 alloys have been researched and manufactured; all these alloys are suitable for application in the metal hydride compressor.
(2) We have installed a metal hydride compressor system with special characteristics; this system was composed of six parts, with autocontrol by a microcomputer; it can operate continuously for a long time. (3) This system has been applied in cryogenic technology, when coupled with a J - T cooler in a closed cycle; a cooling capacity of 0.4W at 25K was obtained, and a cooling capacity of 1.35 W at 77 K when coupled with a G - M cooler in an open cycle test.
References [1] J.A. Jones and P.M. Golben, Cryogenics, 25 (1985) 212-219. [2] K. Karperos, Proc. 4th Int. Cryocooler Conf., 1986, pp. 1-29. [3] S. Bard et al., Proc. 7th Int. Cryocoolers Conf., Santa Fe, NM, 17-19 November 1992, 1992. [4] R.C. Bowman, Cryogenic Engineering and Cryogenic Materials Conf., Vol. 39, NM, 1993, 1993, pp. 1499-1506. [5] L.A. Wade, Cryogenic Engineering and Cryogenic Materials
Conf., Vol. 39, NM, 1993, pp. 1491-1498.
[6] Z. Feng, Z. Liang et al., Gao Ji Shu Tong Shun, 1 (8) (1991)
20-24 (in Chinese).
A~OYS AHD COMPOUHDS ELSEVIER
Journal of Alloys and Compounds 231 (1995) 907-909
Metal hydride compressor and its application in cryogenic technology Zhan Feng a, F|ao Deyou a, Jiang Lijun a, Zhang Liang b, Yu Xiaoyu b, Zhou Yiming b ~General Research ]nstitutefor Nonferrous Metals, 2 Xin Jie Kou Wai Street, Beijing 100088, People's Republic of China bCryogenic Laboratory, Chinese Academy of Sciences, Zhong guan cun, Beijing 100080, People's Republic of China
Abstract
The AB 2 and AB 5 type,; of hydrogen storage alloy have been investigated for meeting the requirements of making a metal hydride compressor with some characteristics applied in the cryogenic technology. Using this compressor, a cooling capacity of 0.4 W at 25 K was obtained with a Joule-Thomson microcooler, and 1.35 W at 77 K with a small G-M cooler was also tested. Keywords: Metal hydrides; Hydrogen compressor; Cryogenics;Liquid hydrogen;Joule-Thomson effect
1. Introduction The metal hydride ]hydrogen storage alloy is a functional material which can realize an energy transformation process to form a sorption compressor with the advantages of no moving parts, little vibration, without noise, long cycling life and use of low grade heat as the power, A sorption compressor has been developed and tested. A cooling capacity of 0.4 W at 25 K was obtained with a Joule-Thompson (J-T) loop, precooled by liquid nitrogen, which is suitable for application in aerospace, IR and space surveillance etc. [1-5]. This compressor was also coupled with a small G - M refrigerator running at 7 7 K with 1.35W cooling power, which is useful for superconductor research, electronic apparatus and cryosurgery equipment [6].
2. E x p e r i m e n t s
2.1. Properties o f hydrogen storage alloy for the compressor
developed an AB 2 type of titanium series Laves phase alloys such as Ti0.77Zr0.23(MnCrCu)z (alloy 1) and Ti0.85Zr0.15(MnCrV)2 and also an AB 5 type of LaNi 5 alloy. Fig. 1 shows the P - C - T curve of alloy 1 and Fig. 2 shows the van't Hoff curve for these three alloys. The test results of the single compressor is s h o w n in Table 1 for Ti0.77Zr0.~3(MnCrCu)2 alloy and in Table 2 for LaNi 5 alloy. The equilibrium pressure for the absorption of hydrogen at room temperature for these three alloys is 0.1-0.6 MPa, and the desorption equilibrium hydrogen pressure at 90-100°C is about 1.5-4.0 MPa. l0
"~n
;
O.
"
' x" 0.1 -
• 6 0 C desorption
As a hydrogen storage alloy used in a sorption compressor, besides having a good plateau property, lower hysteresis, easy activation, longer cycling life
zx 40 c obsorption • 4o c desorption 7 3 0 C obsorption x 3 0 C desorption
etc., it must possess a higher capacity of absorption
and desorption, good kJinetic properties in order to obtain a high hydrogen flow rate, suitable pressure difference and high pressure ratio at operating ternperatures. On the basis of these requirements, w e 0925-8388/95/$09.50 © 1995 Elsevier Science S.A. All rights reserved SSD1 0925-8388(95)01781-X
0 6 0 C absorptio
°°10
I
I
I
I
I
I
I
I
I
0.1 0.20.3 0.4 0.5 0.6 0.7 0.8 0.9 H/M Fig. 1. P-C-T curve for alloy 1.
I
I
.I
Z. Feng et al. / Journal of Alloys and Compounds 231 (1995) 907-909
908 10
pressors, three inlets, three auto-outlet valves and 12 solenoid valves controlled by a microcomputer, could supply a continuous hydrogen steam at a high pressure and suck in hydrogen at a low pressure when it circulated back from a J - T refrigerator or a G - M
o "l-i0.83Zr0A5(MnCrV)2 • TiO,77ZrO.23(MnCrCu)2 Iq LaNI5
z~
I
O. I 2.7
I 2.8
I 2.9
I I 3 3.1 1000/T(K)
I 3.2
I 3.3
Fig. 2. The van't Hoff curves for the three alloys, Table 1
The test results of the single compressor with Tio.77Zro23(MnCrCu)z alloy, Absorption conditions
cooler Every single compressor set is filled in with 0.8 Kg of alloy using a special packing m e t h o d in order to improve the thermal conductivity in the sorption bed. The thickness of this bed is 5 mm. T h e hot water at about 95 °C and the running water at r o o m temperature, used as heating and cooling media respectively, pass through both sides of the annular bed to enhance the heat transfer between the compressor and the water. The three compressors are installed in the compressor system with self-sealing fittings. The hydride compressor system includes six parts: metal hydride compressor sets, hydrogen source, fluid cycling loop, water circulation system, microcomputer control system and m e a s u r e m e n t system.
Desorption properties
P (MPa)
T (°C)
t emax T (min) ( M P a ) (°C)
Q" (1)
V (ml g ~min t)
0.3 0.3 0.4 0.6 0.6
18 8 7 18 8
3 3 3 3 3
33 74 96 59 90
11.1 24.9 32.3 19.9 30.3
2.2 2.7 3.4 4.2 4.5
90 97 99 99 92
a Total desorption amounts of hydrogen for 1 cycle, The absorption capacity at low temperatures and low pressures is 25-40 ml g min -1. It could require a metal hydride compressor with a hydrogen flow rate of 201min -1 and refrigeration t e m p e r a t u r e of 25 K.
2.2. Hydride compressor system The equilibrium pressures of the hydrogen storage alloy, which reacts with hydrogen at different temperatures, are different. After repeated reciprocal heating and cooling, the hydrogen storage material can realize the compressor function of absorption at low pressures (inlet) and desorption at high pressures (outlet). The h y d r i d e - h y d r o g e n compressor system is shown in fig. 3. This system, formed with three single com-
2.3. Application in the 25 K liquid-hydrogen temperature cryogenic technology The metal hydride compressor filled with the LaNi 5 alloy was coupled to a J - T cooler pre-cooled by liquid nitrogen. The cooling capacity of 0.4 W was measured after 95 min in closed cycling, when the inlet pressure is 1.4 MPa, the outlet pressure is 0.3 M P a and the flow rate is 201 min -1. Fig. 4 shows the decrease in temperature with time.
2.4. A application in the 7 7 K G - M refrigerator T o obtain liquid-nitrogen t e m p e r a t u r e from r o o m t e m p e r a t u r e with this compressor system, a G - M refrigerator was developed. A refrigeration power of 1.35 W at 77 K is obtained in an open-loop test when the inlet pressure is 2.0 MPa, and the outlet pressure is 0.6 MPa. It can be used in the m e a s u r e m e n t of the critical t e m p e r a t u r e of a superconductor with the benefits of realizing continuous m e a s u r e m e n t of the electrical properties of it was high accuracy, easy operation and quick measurement.
Table 2 The test results of the single compressor with LaNisalloy. Compressor
1 2 3
Absorption conditions
Desorption properties
P (MPa)
T (°C)
t
Pmax
(min)
(MPa)
T (°C)
Qa (1)
V (mlg t min ~)
0.3 0.3 0.3
15.5 14.5 15.5
3 3 3
2.6 2.4 2.4
97.5 95 93
80 75 94
30.7 28 35.6
a Total desorption amounts of hydrogen for 1 cycle.
Z. Feng et al. / Journal of Alloys and Compounds 231 (1995) 907-909
GH2 supplyvolve [
J Hot water JI Coolwaterin I t~re'erv°ir Check valve ,- ...... ~SvOo;y ~ ~jl~~
Low pressure
hadingtank
r, ,eo e
909
l
valve
Hiolghing ts::~e
C°°~utater
Fig. 3. The metal hydride compressor system.
w5o v ~-
Liquirange dhydrogen
I00
~,
~ Ir~ ~
50
20o
25
~ Time(min)
50
75
~O 0
,~
Fig. 4. J - T cryogenic temperature lowering curve.
3. Conclusions
(1) AB2-type
Ti~.vTZro.23(MnCrCu)z
and
Ti0.85Zr0.15(MnCrV)2 and ABs-type LaNi 5 alloys have been researched and manufactured; all these alloys are suitable for application in the metal hydride compressor.
(2) We have installed a metal hydride compressor system with special characteristics; this system was composed of six parts, with autocontrol by a microcomputer; it can operate continuously for a long time. (3) This system has been applied in cryogenic technology, when coupled with a J - T cooler in a closed cycle; a cooling capacity of 0.4W at 25K was obtained, and a cooling capacity of 1.35 W at 77 K when coupled with a G - M cooler in an open cycle test.
References [1] J.A. Jones and P.M. Golben, Cryogenics, 25 (1985) 212-219. [2] K. Karperos, Proc. 4th Int. Cryocooler Conf., 1986, pp. 1-29. [3] S. Bard et al., Proc. 7th Int. Cryocoolers Conf., Santa Fe, NM, 17-19 November 1992, 1992. [4] R.C. Bowman, Cryogenic Engineering and Cryogenic Materials Conf., Vol. 39, NM, 1993, 1993, pp. 1499-1506. [5] L.A. Wade, Cryogenic Engineering and Cryogenic Materials
Conf., Vol. 39, NM, 1993, pp. 1491-1498.
[6] Z. Feng, Z. Liang et al., Gao Ji Shu Tong Shun, 1 (8) (1991)
20-24 (in Chinese).