HYDROGEN OCCLUSION CARTRIDGE

Abstract

A hydrogen storage cartridge small and lightweight allows storage and discharge of hydrogen at low pressure and normal temperature. It also can effectively absorb the volume expansion accompanying atomization of a hydrogen storage alloy that occurs due to repeated storage and discharge of hydrogen, and therefore a hydrogen storage cartridge (A) is provided in which deformation due to repeated use, and in particular irregular deformation, extremely unlikely, also it can effectively avoid hydrogen storage irregularities of the hydrogen storage alloy. The hydrogen storage cartridge (A) is used for storage of hydrogen contained in biomass thermal decomposition gas, wherein the material of the hydrogen storage cartridge (A) is pure titanium, and the hydrogen storage cartridge (A) includes in the interior space (1), as a hydrogen storage alloy, at least one hydrogen storage alloy selected from the group comprising lanthanum mischmetal/nickel, titanium/iron, calcium/nickel, and lanthanum/nickel.

Claims

1. A hydrogen occlusion cartridge used for occluding hydrogen recovered from a biomass pyrolysis gas, wherein a material for the hydrogen occlusion cartridge is pure titanium, and an inner space of the hydrogen occlusion cartridge contains one or more selected from a group consisting of a lanthanum mischmetal-nickel type hydrogen occlusion alloy, a titanium-iron type hydrogen occlusion alloy and a calcium-nickel type hydrogen occlusion alloy as hydrogen occlusion alloys.

2. The hydrogen occlusion cartridge according to claim 1, wherein a shape of the inner space of the hydrogen occlusion cartridge is substantially rectangular parallelepiped, the inner space of the hydrogen occlusion cartridge comprises a plurality of chambers for accommodating the hydrogen occlusion alloy, which are separated by at least one partitioning plate, a dimension of the partitioning plate in a longitudinal direction is 70 to 80% of a total length of a dimension of the inner space of the hydrogen occlusion cartridge in the same direction as the longitudinal direction of the partitioning plate, and a dimension of the partitioning plate in a transverse direction is equal to a total length of a dimension of the inner space of the hydrogen occlusion cartridge in the same direction as the transverse direction of the partitioning plate.

3. The hydrogen occlusion cartridge according to claim 1, wherein a shape of the inner space of the hydrogen occlusion cartridge is substantially rectangular parallelepiped, the inner space of the hydrogen occlusion cartridge comprises a plurality of chambers for accommodating the hydrogen occlusion alloy, which are separated by at least one partitioning plate, a dimension of the partitioning plate in a longitudinal direction is 70 to 80% of a total length of a dimension of the inner space in the same direction as the longitudinal direction of the partitioning plate, a dimension of the partitioning plate in a transverse direction is equal to a total length of a dimension of the inner space in the same direction as the transverse direction of the partitioning plate, and the partitioning plate is substantially flat-shaped and substantially perpendicular to each face of the inner space of the hydrogen occlusion cartridge.

4. The hydrogen occlusion cartridge according to claim 2, the number of the plurality of chambers is 2 to 10.

5. The hydrogen occlusion cartridge according to claim 1, wherein the hydrogen occlusion alloy is one or more selected from a group consisting of LmNi.sub.4.73Mn.sub.0.12Al.sub.0.15 (lanthanum mischmetal-nickel 4.73 type), TiFe.sub.0.9 Mn.sub.0.1 (titanium-iron 0.9 type), Fe.sub.0.94Ti.sub.0.96 Zr.sub.0.04Nb.sub.0.04 (titanium-iron 0.94 type), CaNi.sub.5 (calcium-nickel type), and Lm-Ni type alloy (3) (lanthanum mischmetal-nickel type).

6. The hydrogen occlusion cartridge according to claim 3, the number of the plurality of chambers is 2 to 10.

7. The hydrogen occlusion cartridge according to claim 2, wherein the hydrogen occlusion alloy is one or more selected from a group consisting of LmNi.sub.4.73Mn.sub.0.12Al.sub.0.15 (lanthanum mischmetal-nickel 4.73 type), TiFe.sub.0.9Mn.sub.0.1 (titanium-iron 0.9 type), Fe.sub.0.94Ti.sub.0.96Zr.sub.0.04Nb.sub.0.04 (titanium-iron 0.94 type), CaNi.sub.5 (calcium-nickel type), and Lm-Ni type alloy (3) (lanthanum mischmetal-nickel type).

8. The hydrogen occlusion cartridge according to claim 3, wherein the hydrogen occlusion alloy is one or more selected from a group consisting of LmNi.sub.4.73Mn.sub.0.12 Al.sub.0.15 (lanthanum mischmetal-nickel 4.73 type), TiFe.sub.0.9Mn.sub.0.1 (titanium-iron 0.9 type), Fe.sub.0.94Ti.sub.0.96Zr.sub.0.04Nb.sub.0.04 (titanium-iron 0.94 type), CaNi.sub.5 (calcium-nickel type), and Lm-Ni type alloy (3) (lanthanum mischmetal-nickel type).

9. The hydrogen occlusion cartridge according to claim 4, wherein the hydrogen occlusion, alloy is one or more selected from a group consisting of LmNi.sub.4.73Mn.sub.0.12Al.sub.0.15 (lanthanum mischmetal-nickel 4.73 type), TiFe.sub.0.9Mn.sub.0.1 (titanium-iron 0.9 type), Fe.sub.0.94Ti.sub.0.96Zr.sub.0.04Nb.sub.0.04 (titanium-iron 0.94 type), CaNi.sub.5 (calcium-nickel type), and Lm-Ni type alloy (3) (lanthanum mischmetal-nickel type).

Description

BRIEF DESCRIPTION OF DRAWINGS

[0038] FIG. 1 illustrates an appearance drawing showing one embodiment of a hydrogen occlusion cartridge according to the present invention.

[0039] FIG. 2 illustrates a front view of the hydrogen occlusion cartridge shown in FIG. 1 from the view of a side of hydrogen ports, a I-I sectional view, and a II-II sectional view.

DESCRIPTION OF EMBODIMENTS

[0040] The material for the hydrogen occlusion cartridge according to the present invention is pure titanium, preferably pure titanium 2. Thereby deformation and distortion of the cartridge itself due to heat generation and heat absorption during hydrogen occlusion and emission can be reduced. In addition, the hydrogen occlusion cartridge according to the present invention has an inner space thereinside, and the inner space includes, as the hydrogen occlusion alloys, one or more selected from a group consisting of a lanthanum mischmetal-nickel type hydrogen occlusion alloy a titanium-iron type hydrogen occlusion alloy and a calcium-nickel type hydrogen occlusion alloy. Preferably, one or more selected from a group consisting of LmNi.sub.4.73Mn.sub.0.12Al.sub.0.15 (lanthanum mischmetal-nickel 4. 73 type), TiFe.sub.0.9Mn.sub.0.1 (titanium-iron 0.9 type). Fe.sub.0.94Ti.sub.0.96Zr.sub.0.04Nb.sub.0.04 (titanium-iron 0.94 type), CaNi.sub.5 (calcium-nickel type), and Lm-Ni type alloy (3) (lanthanum mischmetal-nickel type) are included. Use of these hydrogen occlusion alloys makes it possible too occlude and emit hydrogen at relatively low pressure and normal temperature (25 C.). The hydrogen occlusion press is preferably 0.15 to 0.6 MPa, more preferably 0.3 to 0.4 MPa. The hydrogen occlusion temperature is preferably 80 to 30C., meanwhile the hydrogen emission temperature is preferably 0 to 100 C. More preferably, both the hydrogen occlusion and hydrogen emission are carried out at ambient temperature e.g. normal temperature (25 C.). However, since the hydrogen occlusion alloy generates heat during hydrogen occlusion, the hydrogen occlusion and hydrogen emission can also be carried out at the temperature within the above range while cooling with water ice bath. On the other hand, since the hydrogen occlusion alloy absorbs heat during hydrogen emission, the hydrogen occlusion and hydrogen emission can also be carried out at the temperature within the above range while heating with a hot water bath, preferably at 80 to 90 C. Herein, since the hydrogen occlusion temperature and the hydrogen emission temperature depend on an occlusion rate of hydrogen to the hydrogen occlusion alloy and an emission rate of hydrogen from the hydrogen occlusion alloy, the hydrogen occlusion temperature and the hydrogen emission temperature can be controlled to appropriate temperatures by appropriately adjusting the hydrogen occlusion rate and the hydrogen emission rate. For example, when hydrogen is collectively occluded into the hydrogen occlusion alloy at a factory or the like, the occlusion can be efficiently carried out by increasing the hydrogen occlusion rate while cooling the hydrogen occlusion cartridge. On the other hand, when the hydrogen occlusion cartridge is used e.g. for a portable information terminal device such as a smartphone, the emission rate of hydrogen emitted from the hydrogen occlusion alloy is low, therefore the hydrogen emission temperature i.e. temperatures of the hydrogen occlusion cartridge and the smartphone themselves are not rapidly decreased, and their temperatures are somewhat lower than normal temperature (25 C.), and rather the temperatures are advantageous because an effect of cooling the smartphone itself can be expected. In relation to the particle size of the hydrogen occlusion alloy at the initial charging, a maximum particle diameter is preferably 1 mm or less. The hydrogen occlusion alloy is pulverized by repeating occlusion and emission of hydrogen.

[0041] Hereinafter, the hydrogen occlusion cartridge according to the present invention will be explained with reference to FIGS. 1 and 2. Herein, FIG. 1 illustrates an appearance drawing showing one embodiment of a hydrogen occlusion cartridge according to the present invention, and FIG. 2 illustrates a front view, a I-I sectional view, and a sectional view of the hydrogen occlusion cartridge shown in FIG. 1 viewed from the side of hydrogen ports. The hydrogen occlusion cartridge (A) according to the present invention shown in FIG. 1 comprises two hydrogen ports (a, b). Hydrogen is supplied from the hydrogen ports (a, b), and occluded to the hydrogen occlusion alloy charged in the hydrogen occlusion cartridge (A). When hydrogen is occluded into the hydrogen occlusion alloy, hydrogen is usually supplied from one hydrogen port e.g. port (a), and at this time, the other hydrogen port e.g. port (b) is closed. Then, hydrogen is supplied to the cartridge (A) while maintaining the aforementioned hydrogen occlusion pressure and temperature. Although the hydrogen supply rate is determined depending on an airier space volume of the hydrogen occlusion cartridge (A), an amount of the hydrogen occlusion alloy, and the like, it is preferably 0.1 to 3 L/min, more preferably 0.5 to 1 L/min. As such, hydrogen occluded into the hydrogen occlusion alloy is connected to an apparatus using hydrogen e.g. a portable information terminal device, an electric automobile, a drone, or the like fore use, maintained at the aforementioned hydrogen emission pressure and temperature, and entitled depending on each amount of hydrogen used in the apparatuses using hydrogen. When emitting hydrogen, hydrogen is usually emitted from the hydrogen port other than the port which has supplied hydrogen e.g. the port (b). Of course, the present invention is not limited to this aspect.

[0042] In the hydrogen occlusion cartridge (A) according to the present invention, both its external shape and the shape of the inner space (1) are preferably substantially rectangular parallelepiped. The external shape may variously changed depending on the shape of the apparatus using hydrogen to which the hydrogen occlusion cartridge (A) is attached. In addition, the inner space (1) of the hydrogen occlusion cartridge (A) is divided by at least one partitioning plate (2) and comprises a plurality of chambers (3) for accommodating the hydrogen occlusion alloy. In relation to the plurality of chambers (3), the inner space (1) of the hydrogen occlusion cartridge (A) comprises preferably 2 to 10 chambers, more preferably 2 to 7 chambers, even more preferably 2 to 5 chambers, still more preferably 3 to 5 chambers. If the inner space (1) of the hydrogen occlusion cartridge (A) is not divided by the partitioning plate (2) and the number of the chambers (3) is only one, when the hydrogen occlusion alloy is pulverized and expanded in volume by repeating occlusion and emission of hydrogen, the hydrogen occlusion alloy is biased in the inner space (1) of the hydrogen occlusion cartridge (A), and therefore hydrogen occlusion unevenness is likely to be caused in recharging hydrogen. In addition, once the hydrogen occlusion alloy is biased, deformation or distortion is readily caused on a part of the hydrogen occlusion cartridge (A) by volumetric expansion of the hydrogen occlusion alloy on the part so that the apparatus may be deformed and destroyed when the cartridge is used in connection with an apparatus using, hydrogen e.g. a portable information terminal device or the like. When a plurality of preferably 2 or more, more preferably 3 or more chambers (3) are provided as described above, the hydrogen occlusion alloy can be dispersed in the plurality of chambers (3) and freely move among the chambers (3) to prevent bias of the hydrogen occlusion alloy. As a result, influence of the expanded hydrogen occlusion alloy can be effectively absorbed, and deformation and distortion of the hydrogen occlusion cartridge (A) can be prevented. Also, the hydrogen occlusion unevenness of the hydrogen occlusion alloy can be prevented. It is unpreferable that the number of the chambers (3) for accommodating the hydrogen occlusion alloy is above the aforementioned upper limit because the manufacturing cost of the hydrogen occlusion cartridge (A) increases, and besides that, bias of the hydrogen occlusion alloy cannot be prevented in some cases. Herein, the charged amount of the hydrogen occlusion alloy is preferably 70 to 95% by volume, more preferably 80 to 90% by vol volume of the total volume of the inner space of the hydrogen occlusion cartridge (A). If the charged amount of the hydrogen occlusion alloy is too high, bias of the alloy cannot be prevented due to expansion of the hydrogen occlusion alloy in some cases. It is preferable that the hydrogen occlusion alloy is almost uniformly dispersed in the plurality of chambers (3), and typically the hydrogen occlusion alloy occupies preferably 70 to 95% by volume, more preferably 80 to 90% by vohmie of the inner space volume of each chamber (3).

[0043] A dimension (l) of the partitioning plate (2) in a longitudinal direction is preferably 70 to 80%, more preferably 73 to 77% of a total length of a dimension (L) of the inner space (1) of the hydrogen occlusion cartridge (A) in the same direction as a longitudinal direction of the partitioning plate (2). If the dimension (l) of the partitioning plate (2) in the longitudinal direction exceeds the aforementioned upper limit, the particulate or powdery hydrogen storage alloy cannot smoothly pass through the spaces between the partitioning plate (2) and the face of the inner space (1) of the hydrogen occlusion cartridge (A), and it becomes impossible to prevent bias of the hydrogen occlusion alloy in the inner space (1) in some cases. On the other hand, if the dimension (l) of the partitioning plate (2) in the longitudinal direction is below the aforementioned lower limit, the partitioning plate (2) cannot sufficiently play the role for itself, and similarly it becomes impossible to prevent bias of the hydrogen occlusion alloy in some cases. Also, a dimension (m) of the partitioning plate (2) in a transverse direction is equal to a total length of a dimension (M) of the inner space (1) of the hydrogen occlusion cartridge (A) in the same direction as the transverse direction of the partitioning plate (2). Thereby, the inner space (1) of the hydrogen occlusion cartridge (A) is completely wailed in the transverse direction of the partitioning plate (2) i.e. in the thickness direction of the inner space (1) of the hydrogen occlusion cartridge (A), to form each chamber. In addition, it is preferable that the partitioning plate (2) is substantially flat-shaped and substantially perpendicular to each face of the inner space (1) of the hydrogen occlusion cartridge (A). When a plurality of partitioning plates (2) are provided, it is preferable that the partitioning plates (2) are substantially parallel to each other, and located so that the dimensions (volumes) of the inner spaces (1) are substantially equal to each other.

[0044] The hydrogen occlusion cartridge according to the present invention is used for occluding hydrogen recovered from a biomass pyrolysis gas. Herein, the biomass is not particularly limited if it is described in Patent Document 4, but includes e.g. a waste material from palm tree (empty fruit bunch: EFB, EFB fiber, palm kernel shell), coconut shell, coconut husk, a waste material from Jatropha tree, an unused waste wood from forests, a sawmill waste from a sawmilling factory, waste paper, rice straw, rice husk, food residue from a food factory, algae, sewage sludge, organic sludge, and the like. In addition, hydrogen recovered from a biomass pyrolysis gas includes hydrogen recovered from a biomass pyrolysis gas obtained by pyrolyzing the above-descried biomass, hydrogen recovered from a biomass obtained by further reforming the pyrolysis gas, or the like. Methods and apparatuses for producing the pyrolysis gas by heat-treating the above-described biomass are known. The following methods are given as examples: a method comprising: heat-treating biomass such as organic waste at 500-600 C. under a non-oxidizing atmosphere; mixing the generated pyrolysis gas with steam at 900-1,000 C.; and purifying the resulting reformed gas to recover hydrogen (Patent Document 4); or a method for gasifying organic waste, comprising: heat-treating organic waste at 400-700 C. under a non-oxidizing atmosphere; mixing the generated pyrolysis gas with steam at 700-1,000 C.; and purifying the resulting reformed gas to produce hydrogen-containing gas, wherein: purifying the reformed gas is carried out by passing the reformed gas through a layer containing aluminum oxide and/or a formed article thereof and kept at 400-700 C. and then further passing the resulting gas through a layer containing one or more substances selected from a group consisting of zinc oxide, iron oxide, calcium oxide and formed articles thereof and kept at 350-500 C.; and subsequently the reformed gas after the purification is passed through a shift reaction catalyst layer at 200-500 C. (Patent Document 5). Furthermore, a method for separating hydrogen from the gas thus obtained and purifying the gas is also known. Other than the above-described method, a method for separating hydrogen by using PSA etc. or the like is known, for example.

[0045] The hydrogen occlusion cartridge according to the present invention can be connected to an apparatus using hydrogen, and can be used as a power source for an apparatus using hydrogen e.g. a portable information terminal devices such as a smartphone or as a power source for an electric automobile, drone and the like, by emitting hydrogen occluded to a hydrogen occlusion alloy charged into the cartridge. Also, the hydrogen occlusion cartridge can be used as a small-sized battery by installing a small fuel cell, an electric capacitor or the like in the inner space of the hydrogen occlusion cartridge.

[0046] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by these Examples.

EXAMPLE 1

[0047] A hydrogen occlusion cartridge (A) made of pure titanium 2 having the shapes and dimensions shown in FIGS. 1 and 2 was prepared. As shown in FIG. 2, the hydrogen occlusion cartridge (A) had substantially rectangular parallelepiped external shape and inner space (1), and the dimension of the cartridge (A) was 41.80 mm in length, 61.60 mm in width, and 7.60 mm in thickness, and the dimension was substantially equal to that of a general smartphone lithium ion battery. The dimension of the inner space (1) of the cartridge (A) was 36 mm in length, 60 mm in width, and 6 mm in thickness, and the inner space (1) was almost uniformly divided in the lateral direction by 3 partitioning plates (2) substantially parallel to each other, and had 4 chambers (3) for accommodating the hydrogen occlusion alloy. All of the partitioning plates (2) were substantially flat-shaped and substantially perpendicular to each face of the inner space (1) of the hydrogen occlusion cartridge (A). The dimension (l) of each partitioning plate (2) in the longitudinal direction was 27 mm, and the total length (L) of the dimension of the cartridge inner space (1) in the same direction as the longitudinal direction of the partitioning plate (2) (lengthwise direction of the inner space (1)) was 36 mm. As described above, the dimension (l) of the partitioning plate (2) in the longitudinal direction was 75% of the total length (L) of the dimension of the cartridge inner space (1) in the same direction as the longitudinal direction of the partitioning plate (2) (lengthwise direction of the inner space (1)). On the other hand, the dimension of the partitioning plate (2) in the transverse direction was 6 mm,which was equal to the total length (M) of 6 mm of the dimension of the cartridge inner space (1) in the same direction as the transverse direction of the partitioning plate (2) (thickness direction of the inner space (1)). All of the partitioning plates (2) had such a shape that a width (n) of a part close to the center was 2.2 mm and the width was somewhat widened toward both ends. In addition, the internal volumes of the individual chambers (3) for accommodating the hydrogen occlusion alloy were substantially equal to each other and the total volume of the 4 chambers was about 8 cc. The total eight of the hydrogen storage cartridge (A) was about 38 g. This weight was about 30% of a weight (about 133 g) of a hydrogen occlusion cartridge made of stainless steel (SUS304) having the same shape and dimension.

[0048] In the 4 chambers (3) in the hydrogen occlusion cartridge (A) made of pure titanium 2, about 56 g of LmNi.sub.4.73Mn.sub.0.12Al.sub.0.15 as the hydrogen occlusion alloy was charged in such a way that the alloy was dispersed almost evenly in the individual chambers.

[0049] The hydrogen occlusion cartridge (A) was immersed in ice water to maintain a temperature of the entire cartridge (hydrogen occlusion temperature) at about 0 C. Separately, a commercially available hydrogen cylinder (internal volume: 7 m.sup.3, pressure: 15 MPa, purity: 99.9%) was prepared. Subsequently, hydrogen is supplied to the hydrogen occlusion cartridge (A) from the cylinder with a hydrogen supply pressure constantly maintained at 0.4 MPa and a hydrogen supply rate of about 1 L/min to occlude hydrogen to the hydrogen occlusion alloy. At this step, in the latter half of the hydrogen occlusion operation, the hydrogen supply rate was gradually decreased from about 1 L/min at the start, with an increase in pressure in the hydrogen occlusion cartridge (A). At the completion of the hydrogen occlusion, the pressure in the hydrogen occlusion cartridge (A) (hydrogen occlusion pressure) was increased to about 0.4 MPa from an atmospheric pressure at the start of the hydrogen occlusion.

[0050] After hydrogen was occluded as described above, the hydrogen occlusion cartridge (A) was left in a room at about 25 C. to maintain the temperature of the entire cartridge (A) at about 25 C. Subsequently, in the room, hydrogen was emitted from the hydrogen occlusion cartridge (A) at a rate of about 1 L/min. At this step, in the latter half of the hydrogen emission operation, the hydrogen emission rate was gradually decreased from about 1 L/min at the start. At this step, in the end of the hydrogen emission, the pressure in the hydrogen occlusion cartridge (A) was decreased to substantially atmosphere pressure from about 0.4 MPa at the start of the hydrogen emission. The temperature in the hydrogen occlusion cartridge (A) (hydrogen emission temperature) was gradually decreased from about 25C. at the start of the hydrogen emission, in association with the hydrogen emission. At the completion of hydrogen emission, the cartridge was at such a temperature that a cold feeling was given when the cartridge was touched by hand.

[0051] The above operations of hydrogen occlusion and hydrogen emission were repeated three times. At this time, the hydrogen occlusion amount and the hydrogen emission amount in each step are shown in the following Table 1. All of the units of the numerical values in Table 1 are expressed as normal liters.

TABLE-US-00001 TABLE 1 Second Third First Operation Operation Operation Hydrogen Occlusion Ammount 7.972 7.930 8.001 Hydrogen Emission Ammount 7.003 7.245 7.666

[0052] Table 1 clarified that the hydrogen occlusion amount to the hydrogen occlusion cartridge (A) and the hydrogen emission amount from the hydrogen occlusion cartridge (A) were substantially equal even when repeating the operations of hydrogen occlusion and hydrogen emission three times, and the hydrogen occlusion cartridge had a constant performance. In addition, even after three repetitions, no deformation of the hydrogen occlusion can ridge (A) itself was observed. As described above, although the hydrogen occlusion cartridge (A) according to the present invention was compact and lightweight, the cartridge could occlude a large volume of hydrogen, and did not lack performances of hydrogen occlusion and emission even when repeating occlusion and emission, and additionally the cartridge itself was not deformed.

INDUSTRIAL APPLICABILITY

[0053] The hydrogen occlusion cartridge according to the present invention can be easily transported and handled and is safe. In addition, the cartridge can be not only used repeatedly for a long period, but also incorporated in an apparatus using hydrogen and repeatedly used without destruction of the apparatus, and expected to always exhibit a constant performance during use. Hence, in the future, it is greatly expected that the cartridge is incorporated and used not only in a portable information terminal devices e.g. an extremely small-sized device such as a smartphone but also in an electric automobile, drone, or the like.

REFERENCE NUMERALS

[0054] A Hydrogen occlusion cartridge according to the present invention [0055] a Hydrogen port [0056] b Hydrogen port [0057] L Dimension of inner space of hydrogen occlusion cartridge in the same direction as longitudinal direction of partitioning plate [0058] l Dimension of partitioning plate in longitudinal direction [0059] M Dimension of inner space of hydrogen occlusion cartridge in the same direction as transverse direction of partitioning plate [0060] m Dimension of partitioning plate in transverse direction [0061] n Width of partitioning plate [0062] 1 Inner space of hydrogen occlusion cartridge [0063] 2 Partitioning plate [0064] 3 Chambers for accommodating hydrogen occlusion alloy