TWI448421B - Porous hydrogen generating material and manufacturing method thereof - Google Patents

Description

Porous hydrogen production material and method of producing the same

The present invention relates to a porous hydrogen producing material and a method for producing the same, and particularly relates to a porous hydrogen producing material which is excellent in hydrophilicity and simple in production flow, and a method for producing the same.

In general, fuel cells use hydrogen to make electricity. The only by-products that are produced are pollution-free water and hot gas, which is why many people see it as an energy source that can replace oil. Furthermore, hydrogen energy is actively invested in advanced countries based on energy security and environmental sustainability due to its cleanliness and storability. At present, the use of hydrogen energy is mainly through the fuel cell device to turn chemical energy into electrical energy, and its applications cover distributed power generation systems, transportation vehicles and portable 3C products. However, fuel cells are still some distance away from commercialization, mainly due to the storage and supply of hydrogen and the cost of fuel cells still not in line with commercial needs.

In view of the above, in order to supply hydrogen gas to act as a raw material for a fuel cell, the production of hydrogen has become a very important issue. At present, there are many researches and developments on hydrogen production materials, many of which use water as a source of hydrogen production. Generally, hydrogen-generating materials include a carrier, a hydrogen-generating agent, and a catalyst. After water is added to the hydrogen-generating material, the catalyst is catalyzed to generate hydrogen. However, the conventional carrier is usually selected from a powder structure, and the compact structure of the powder causes poor water permeability of the hydrogen producing material and causes a decrease in hydrogen production efficiency. In addition, the general powder structure will be in the process of hydrogen production. It is easy to disintegrate, and the catalyst in the carrier is not easily recycled and reused, resulting in an increase in manufacturing cost.

The present invention provides a porous hydrogen producing material comprising a porous carrier composed of fibers, and thus having good hydrophilicity and a strong porous structure.

The present invention further provides a method for producing a porous hydrogen producing material, which has a simple manufacturing process.

The present invention provides a porous hydrogen producing material comprising a fibrous carrier, a hydrogen generating agent, and a hot melt. The fibrous carrier comprises a plurality of fibers stacked on each other with a plurality of pores between the fibers. The hydrogen generating agent is dispersed on the fibers of the fiber carrier. The hot melt adheres the fibers of the fiber carrier and the hydrogen generating agent together.

In an embodiment of the invention, the fibrous carrier comprises an ionic fibrous carrier.

In one embodiment of the invention, the ionic fibrous carrier comprises a natural water soluble polymeric carrier, a modified natural polymeric carrier or a synthetic polymeric carrier.

In an embodiment of the invention, the hydrogen generating agent comprises NaBH ₄ , NH ₃ BH ₃ , MgH ₂ or C ₁₀ H ₁₈ .

In an embodiment of the invention, the hot melt comprises polyethylene (PE), ethylene vinyl acetate (EVA), polyurethane (TPU) or polyethylene terephthalate (PET). .

In an embodiment of the invention, the fiber carrier and the hydrogen generating agent are And the weight ratio of hot melt is 1.5:4:1.5.

The present invention further provides a method of producing a porous hydrogen producing material comprising the following steps. A fiber carrier, a hydrogen generator, and a hot melt are provided. The fibrous carrier, the hydrogen generating agent, and the hot melt are uniformly mixed to form a mixed material. The mixed material is subjected to a heat treatment process to form a porous hydrogen producing material.

In an embodiment of the invention, the method of manufacturing the fibrous carrier comprises the following steps. A fiber solution was prepared. A cobalt-containing coagulation bath was prepared. The fiber solution is placed in a spinning apparatus to perform a weaving process in which the spinning apparatus squeezes the fiber solution into a cobalt-containing coagulation bath to form long fibers by mechanical spinning.

In an embodiment of the invention, the fiber solution comprises an ionic fiber solution.

In an embodiment of the invention, the ionic fiber solution comprises a natural water-soluble polymer solution, a modified natural polymer solution or a synthetic polymer solution.

In an embodiment of the invention, the above natural water-soluble polymer solution comprises a cellulose solution, a starch solution, a chitosan chitin solution or a sodium alginate solution. The modified natural polymer solution includes a modified starch solution and a modified cellulose solution, wherein the modified starch solution comprises a carboxymethyl starch solution or a starch acetate solution, and the modified cellulose solution comprises a hydroxymethyl cellulose solution or a carboxy group. Methylcellulose solution. The above synthetic polymer solution includes a polymer resin solution or a condensed resin solution having an anionic group, wherein the anionic group includes a carboxylic acid group, a sulfonic acid group, a phosphoric acid group or a sulfuric acid group.

In an embodiment of the invention, the concentration of the fiber solution is 2% to 5% by weight.

In an embodiment of the invention, the cobalt-containing coagulation bath comprises a cobalt chloride coagulation bath.

In an embodiment of the present invention, the concentration of the cobalt-containing coagulation bath is 5% to 55% by weight (saturated concentration at room temperature), and preferably, the concentration of the cobalt-containing coagulation bath is preferably 10 %~25%.

In an embodiment of the invention, the hydrogen generating agent comprises NaBH ₄ , NH ₃ BH ₃ , MgH ₂ or C ₁₀ H ₁₈ .

In an embodiment of the invention, the hot melt comprises polyethylene (PE), ethylene vinyl acetate (EVA), polyurethane (TPU) or polyethylene terephthalate (PET). .

In an embodiment of the invention, the heat treatment procedure described above comprises the steps described below. The mixed material is placed in a mold. Perform a compression molding process. Perform a heat setting procedure.

In one embodiment of the invention, the weight ratio of the above fibrous carrier, hydrogen generating agent and hot melt is 1.5:4:1.5.

Based on the above, the porous hydrogen producing material of the present invention comprises a hydrophilic fibrous carrier and has good hydrophilicity. In addition, the pores in the porous fibrous support provide a suitable space for the water to react with the hydrogen generating agent. Further, the porous hydrogen producing material of the present invention has sufficient mechanical strength and its structure is not easily damaged. Further, the method for producing a porous hydrogen producing material of the present invention has a property of being simple to manufacture.

The above described features and advantages of the present invention will be more apparent from the following description.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing a method of producing a porous hydrogen producing material according to an embodiment of the present invention. Referring to FIG. 1, first, step S10 is performed to provide a fiber carrier, a hydrogen generating agent, and a hot melt. The weight ratio of the fibrous carrier, the hydrogen generating agent and the hot melt is, for example, 1.5:4:1.5. The fibrous carrier comprises a plurality of fibers stacked on each other, and the fibrous carrier is, for example, an ionic fibrous carrier, and in particular, the ionic fibers have hydrophilic properties. The above ionic fiber carrier is, for example, a natural water-soluble polymer carrier, a modified natural polymer carrier or a synthetic polymer carrier. Further, the above hydrogen generating agent is, for example, NaBH ₄ , NH ₃ BH ₃ , MgH ₂ or C ₁₀ H ₁₈ . The above hot melt agent is, for example, polyethylene (PE), ethylene vinyl acetate (EVA), polyurethane (TPU) or polyethylene terephthalate (PET), and the hot melt compound is listed here. Just for illustration. In general, any polymer compound having a low melting point can be used, and the present invention is not limited thereto.

Next, in step S20, the above-mentioned fibrous carrier, hydrogen generating agent and hot melt are uniformly mixed to form a mixed material.

Finally, in step S30, the above mixed material is subjected to a heat treatment process to form the porous hydrogen producing material 100. In detail, FIGS. 2A to 2D are schematic views showing a manufacturing flow of the heat treatment procedure in step S30. Referring to FIGS. 2A to 2D, first, a mixed material X including the above-described fiber carrier 120, hydrogen generating agent 140, and hot melt 160 is placed in a mold A as shown in FIG. 2A. Next, a stamper P1 is performed as shown in Fig. 2B and a heat setting program P2 is performed as shown in Fig. 2C. Finally, move the mold A Alternatively, the fabrication of the porous hydrogen production material 100 can be accomplished, as shown in Figure 2D. Specifically, the molding process P1 can compress the mixed material into a piece of solid. Next, when the heating setting program P2 is performed, the hot melt 160 is melted into a liquid state as the temperature rises, and at this time, the liquid hot melt 160 is interspersed between the fibers 122 and the hydrogen generating agent 140. Then, the cooling action is performed, and the liquid hot melt 160 is solidified, and the hydrogen generating agent 140 and the fibers 122 are adhered together. It should be noted that since the hot melt 160 does not fill all the spaces between the fibers 122 and the hydrogen generating agent 140 in the liquid state, a form having voids is formed after curing.

Here, a method of manufacturing the above fiber carrier 120 will be described, which includes the following steps. First, a fiber solution is prepared. Next, a cobalt-containing coagulation bath was prepared. Finally, the fiber solution is placed in a spinning apparatus to perform a weaving process in which the spinning apparatus extrudes the fiber solution into a cobalt-containing coagulation bath to form long fibers by mechanical spinning. The above textile process is, for example, a wet textile process.

Specifically, the concentration of the fiber solution is, for example, 2% to 5% by weight. It is explained herein that the fiber solution includes a solute and a solvent, and the above concentration refers to a concentration by weight of the solute in the solution. In detail, the fiber solution is, for example, an ionic fiber solution, and the ionic fiber solution is, for example, a natural water-soluble polymer solution, a modified natural polymer solution, or a synthetic polymer solution. Wherein, the above natural water-soluble polymer solution is, for example, a cellulose solution, a starch solution, a chitosan chitin solution or a sodium alginate solution. The modified natural polymer is, for example, a modified starch solution and a modified cellulose solution, wherein the modified starch solution is, for example, a carboxymethyl starch solution or a starch acetate solution, and the modified cellulose solution is, for example, hydroxymethyl cellulose. Solution or carboxymethylcellulose solution. The above synthetic polymer solution is, for example, a polymer-based resin or a condensed resin solution having an anionic group such as a carboxylic acid group, a mineral acid group, a phosphoric acid group or a sulfuric acid group. Further, the above cobalt-containing coagulation bath is, for example, a cobalt chloride coagulation bath. The concentration of the cobalt-containing coagulation bath is, for example, 5% to 55% by weight (saturated concentration at room temperature). It is explained herein that the cobalt-containing coagulation bath includes a solute and a solvent, and the above concentration refers to a concentration by weight of the solute in the solution.

In detail, when the fiber solution is extruded into the cobalt-containing coagulation bath, the cobalt ions in the cobalt-containing coagulation bath are ionically bonded to the fiber solute in the fiber solution, and the otherwise water-soluble fiber solute becomes non-water soluble. Sexual curing fiber. Therefore, cobalt ions are ionic bonded to the surface of the fiber.

Thus, the production of the porous hydrogen producing material 100 is completed. That is, the production of the porous hydrogen producing material 100 of the present invention can be completed by performing only steps S10 to S30. Therefore, the method for producing the hydrogen producing material 100 of the present invention has a simple manufacturing process. What is more worth mentioning is that, in addition to the above-mentioned block shape, the technician can change the mold of different shapes according to the actual needs thereof, that is, the porous hydrogen production material of different shapes can be obtained, and therefore, the porosity of the present invention The method of manufacturing the hydrogen producing material 100 is suitable for practical use.

Fig. 3 is a schematic view showing the structure of a porous hydrogen producing material 100 according to an embodiment of the present invention. 4 is an enlarged plan view showing a partial area M of FIG. 3. Referring to FIG. 3 and FIG. 4, the porous hydrogen production material 100 of the present embodiment includes a fiber carrier 120, a hydrogen generating agent 140, and a hot melt 160. The fiber carrier 120 includes a plurality of fibers 122 stacked on one another with a plurality of apertures 124 between the fibers 122. In other words, when the fibers 122 are stacked on each other At the same time, the fibers 122 form a void with each other, that is, form a three-dimensional space. The fiber carrier 120 is, for example, an ionic fiber carrier. The above ionic fiber carrier is, for example, a natural water-soluble polymer carrier, a modified natural polymer or a synthetic polymer carrier. Also, the fiber carrier 120 has good hydrophilic properties.

The hydrogen generating agent 140 is dispersed on the fibers 122 of the fiber carrier 120. In particular, the hydrogen generating agent 140 is interspersed with pores between the fibers 122, that is, a portion of the hydrogen generating agent 140 is located in the three-dimensional space formed by the stacking of the fibers 122.

The hot melt 160 adheres the fibers 122 of the fiber carrier 120 and the hydrogen generating agent 140 together. In detail, the hot melt 160 is, for example, a low melting point polymer, and the fiber carrier 120 and the hydrogen generating agent 140 can form a porous bulk solid by a heat setting process. Moreover, the bulk solid can have a certain strength. It is not easy to cause the problem of structural disintegration after hydrogen production.

Instance

In order to explain in detail the porous hydrogen producing material of the present invention, an example of the manufacturing process will be described below. First, the production of the fiber carrier is carried out. Table 1 shows the relevant experimental conditions for spinning in this example.

Referring to Table 1, a sodium alginate solution having a concentration of 2% by weight is used as a fiber solution, and the sodium alginate solution is placed in a spinning device and extruded into a cobalt chloride coagulation bath at a concentration of 25% by weight. At this time, the sodium ions in the water-soluble sodium alginate molecule exchange ion exchange with the cobalt ions in the coagulation bath to form a solidified cobalt alginate fiber, and the fiber carrier is completed. This cobalt alginate fiber is water-insoluble and hydrophilic (water absorption). More specifically, after the cobalt alginate fibers are formed, they are again impregnated into the coagulation bath for about 12 hours to increase the cobalt content of the cobalt alginate fibers.

Next, sodium borohydride (NaBH ₄ ) was used as a hydrogen generator, and high density polyethylene (HDPE) was used as a hot melt. The cobalt alginate fiber, sodium borohydride, and high density polyethylene (HDPE) were mixed into a mixed material in a ratio of 1.5:4:1.5 by weight. The mixed material is placed in a mold for compression molding and a heat setting process. Wherein, using a mold for heating and setting at a temperature of 150 ° C for 2 hours, a structure having a plurality of pores between the cobalt alginate fibers is formed, and the hydrogen generating agent is dispersed on the cobalt alginate fibers, and the example is completed. Porous hydrogen production material.

In particular, the porous hydrogen producing material of the present invention is used by directly adding water to the porous hydrogen producing material. Since the porous hydrogen producing material has pores supported by cobalt alginate fibers, sodium borohydride adheres to the cobalt alginate fibers, and cobalt ions in the cobalt alginate fibers can serve as a catalyst. Therefore, when water enters the pores, the pores provide a spatial structure for the water to react with sodium borohydride, and the cobalt ions facilitate the catalytic reaction. Hydrogen is produced. In addition, since the water absorption/water content of the cobalt alginate fiber is very high, it is advantageous to leave moisture on the fiber carrier to improve the hydrogen production efficiency. In addition, the use of high-density polyethylene (HDPE) can provide a porous hydrogen-producing material with sufficient mechanical strength, so that when hydrogen is generated and emerges from the pores, the porous hydrogen-producing material of the present invention is less prone to structural collapse. The situation of the solution.

In view of the above, in order to explain in detail the influence of the content ratio of sodium borohydride, cobalt alginate fiber and hot-melt powder on the porous hydrogen-producing material, Comparative Example 1 and Comparative Example 2 which have different content ratios in Table 2 are exemplified. Description.

Referring to Table 2, the content of the hot-melt powder in the porous hydrogen-producing material of Comparative Example 1 and Comparative Example 2 was lower than that of the example porous hydrogen-producing material. When the water supply test was performed, the porous hydrogen production materials of Comparative Example 1 and Comparative Example 2 collapsed after the generation of hydrogen gas. The example of a porous hydrogen production material maintains a complete structure. It can be seen that when the content ratio of cobalt alginate fiber, sodium borohydride and hot-melt powder is substantially 1.5:4:1.5, the porous hydrogen-producing material can have sufficient mechanical strength to maintain porosity during hydrogen production. structure.

It is worth mentioning that when sodium borohydride reacts with water, it forms a cobalt boron catalyst with cobalt ions in the cobalt alginate fiber. The cobalt boron catalyst can be further used to catalyze the reaction of sodium borohydride with water to generate hydrogen. In other words, when the hydrogen-generating agent of the present invention uses a boron-containing compound such as sodium borohydride (NaBH ₄ ) or borohydride (NH ₃ BH ₃ ), the porous hydrogen-generating material of the present invention may be stepwise. Catalytic reaction, thus having a two-stage hydrogen production reaction, that is, long-term hydrogen production efficiency. In addition, since the cobalt-boron catalyst adheres to the surface of the fiber after formation, it is not easily lost with water, so that the efficiency of hydrogen production can be improved. Further, since the porous hydrogen producing material of the present invention has good mechanical strength, its structure is not easily damaged after hydrogen production, and therefore the cobalt boron catalyst can be recycled again.

Of course, the detailed synthetic procedure for the porous hydrogen-producing material described above, as well as the concentration and amount of various materials, are only intended to enable those skilled in the art to practice the invention and are not intended to limit the invention.

As described above, the porous hydrogen producing material of the present invention comprises a porous fibrous carrier composed of hydrophilic fibers, so that it has good hydrophilicity and provides a suitable space for the water to react with the hydrogen generating agent. In addition, the use of a hot melt allows the porous hydrogen producing material to have sufficient mechanical strength and its structure is not easily damaged. Furthermore, cobalt ions attached to the surface of the fiber and possibly cobalt boron ions can provide a two-stage catalytic hydrogen production efficiency. Therefore, the porous hydrogen producing material of the present invention has a long-acting catalytic hydrogen production efficiency. Further, the method for producing a porous hydrogen producing material of the present invention is relatively simple and convenient to produce.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the invention, and any one of ordinary skill in the art can make some modifications and refinements without departing from the spirit and scope of the invention. this The scope of the invention is defined by the scope of the appended claims.

S10, S20, S30‧‧‧ steps

100‧‧‧Porous hydrogen production materials

120‧‧‧Fiber carrier

122‧‧‧ fiber

124‧‧‧ pores

140‧‧‧ Hydrogen generator

160‧‧‧Hot flux

X‧‧‧ mixed materials

P1‧‧‧ compression molding program

P2‧‧‧heat setting procedure

M‧‧‧ area

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing a method of producing a porous hydrogen producing material according to an embodiment of the present invention.

2A to 2D are schematic views showing a manufacturing process of a heat treatment process.

Fig. 3 is a schematic view showing the structure of a porous hydrogen producing material according to an embodiment of the present invention.

4 is an enlarged plan view showing a partial area M of FIG. 3.

100‧‧‧Porous hydrogen production materials

120‧‧‧Fiber carrier

122‧‧‧ fiber

124‧‧‧ pores

160‧‧‧Hot flux

Claims (20)

A porous hydrogen production material comprising: a fiber carrier comprising a plurality of fibers stacked on each other, the fibers having cobalt ions bonded to the surface thereof and a plurality of pores between the fibers; a hydrogen agent dispersed on the fibers of the fiber carrier; and a hot melt that adheres the fibers of the fiber carrier and the hydrogen generating agent together. The porous hydrogen producing material of claim 1, wherein the fibrous carrier comprises an ionic fibrous carrier. The porous hydrogen producing material according to claim 2, wherein the ionic fibrous carrier comprises a natural water-soluble polymer carrier, a modified natural polymer carrier or a synthetic polymer carrier. The porous hydrogen producing material according to claim 1, wherein the hydrogen generating agent comprises NaBH ₄ , NH ₃ BH ₃ , MgH ₂ or C ₁₀ H ₁₈ . The porous hydrogen producing material according to claim 1, wherein the hot melt comprises polyethylene (PE), ethylene vinyl acetate (EVA), polyurethane (TPU) or polyparaphenylene. Ethylene formate (PET). The porous hydrogen producing material according to claim 1, wherein the fiber carrier, the hydrogen generating agent and the hot melt have a weight ratio of 1.5:4:1.5. A method for producing a porous hydrogen producing material, comprising: providing a fiber carrier, a hydrogen generating agent, and a hot melt agent, wherein the method for manufacturing the fiber carrier comprises: Preparing a fiber solution; preparing a cobalt-containing coagulation bath; and placing the fiber solution in a spinning device to perform a spinning process, wherein the spinning device squeezes the fiber solution into the cobalt-containing coagulation bath to mechanically pump The filaments form long fibers; the fibrous carrier, the hydrogen generating agent and the hot melt are uniformly mixed to form a mixed material; and the mixed material is subjected to a heat treatment process to form a porous hydrogen producing material. The method for producing a porous hydrogen producing material according to claim 7, wherein the fiber solution comprises an ionic fiber solution. The method for producing a porous hydrogen producing material according to claim 8, wherein the ionic fiber solution comprises a natural water-soluble polymer solution, a modified natural polymer solution or a synthetic polymer solution. The method for producing a porous hydrogen producing material according to claim 9, wherein the natural water-soluble polymer solution comprises a cellulose solution, a starch solution, a chitosan chitin solution or a sodium alginate solution. The natural polymer solution comprises a modified starch solution and a modified cellulose solution, wherein the modified starch solution comprises a carboxymethyl starch solution or a starch acetate solution, and the modified cellulose solution comprises a hydroxymethyl cellulose solution or a carboxymethyl group. a cellulose solution, and the synthetic polymer solution comprises a polymer resin solution or a condensed resin solution having an anionic group, wherein the anionic group comprises a carboxylic acid a group, a sulfonic acid group, a phosphoric acid group or a sulfuric acid group. The method for producing a porous hydrogen producing material according to claim 7, wherein the fiber solution has a concentration of 2% to 5% by weight. The method for producing a porous hydrogen producing material according to claim 7, wherein the cobalt-containing coagulation bath comprises a cobalt chloride coagulation bath. The method for producing a porous hydrogen producing material according to claim 7, wherein the concentration of the cobalt-containing coagulation bath is 5% to 55% by weight. The method for producing a porous hydrogen producing material according to claim 13, wherein the cobalt-containing coagulation bath has a concentration of 10% to 25% by weight. The method for producing a porous hydrogen producing material according to claim 7, wherein the hydrogen generating agent comprises NaBH ₄ , NH ₃ BH ₃ , MgH ₂ or C ₁₀ H ₁₈ . The method for producing a porous hydrogen producing material according to claim 7, wherein the hot melt comprises polyethylene (PE), ethylene vinyl acetate (EVA), polyurethane (TPU) or poly Ethylene terephthalate (PET). The method for producing a porous hydrogen producing material according to claim 7, wherein the heat treatment procedure comprises: placing the mixed material in a mold; performing a compression molding process; and performing a heat setting process. The method for producing a porous hydrogen producing material according to claim 7, wherein the fiber carrier, the hydrogen generating agent, and the hot melt are heavy. The ratio is 1.5:4:1.5. The porous hydrogen producing material according to claim 1, wherein the hydrogen generating agent is a boron hydride compound. The method for producing a porous hydrogen producing material according to claim 7, wherein the hydrogen generating agent is a boron hydride compound.