WO2017018378A1 - 水素ガス製造装置及び水素ガス製造方法 - Google Patents
水素ガス製造装置及び水素ガス製造方法 Download PDFInfo
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- WO2017018378A1 WO2017018378A1 PCT/JP2016/071726 JP2016071726W WO2017018378A1 WO 2017018378 A1 WO2017018378 A1 WO 2017018378A1 JP 2016071726 W JP2016071726 W JP 2016071726W WO 2017018378 A1 WO2017018378 A1 WO 2017018378A1
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- gas
- porous body
- hydrogen gas
- mixed gas
- carbon dioxide
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 239000007789 gas Substances 0.000 claims abstract description 259
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 116
- 239000012466 permeate Substances 0.000 claims abstract description 59
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 58
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 58
- 239000011148 porous material Substances 0.000 claims abstract description 44
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 28
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 claims description 24
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 21
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 13
- 230000001186 cumulative effect Effects 0.000 claims description 9
- 239000000919 ceramic Substances 0.000 claims description 7
- 229910010272 inorganic material Inorganic materials 0.000 claims description 7
- 239000011147 inorganic material Substances 0.000 claims description 6
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- 239000001257 hydrogen Substances 0.000 abstract description 3
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- 229910052786 argon Inorganic materials 0.000 description 5
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- 229910052751 metal Inorganic materials 0.000 description 4
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
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- 229910052582 BN Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
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- 229910021426 porous silicon Inorganic materials 0.000 description 1
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- 239000011347 resin Substances 0.000 description 1
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- 230000000717 retained effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
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Definitions
- the present invention relates to a hydrogen gas production apparatus and a hydrogen gas production method.
- Patent Document 1 discloses an example in which a mixed gas composed of hydrogen gas and carbon dioxide gas is caused to flow into a porous body having a thickness of 1 mm under conditions where the inflow pressure is 0.2 to 2 MPa and the outflow pressure is 0.1 MPa. (Refer to page 3 of Patent Document 1 and Example 2).
- the pressure gradient defined as a value obtained by dividing the difference between the inflow pressure and the outflow pressure by the thickness of the porous body is about 100 to 1900 MPa / m.
- This invention is made
- a hydrogen gas production apparatus comprises: A porous body that is permeable to hydrogen gas and carbon dioxide gas, and has a property of allowing hydrogen gas to pass more easily than carbon dioxide gas;
- the porous body is supplied with a mixed gas containing carbon dioxide gas and hydrogen gas, the length of the porous body in the direction in which the mixed gas permeates is L, and the inflow pressure of the mixed gas to the porous body is P. 1.
- a mixed gas source that flows in under a condition that a pressure gradient represented by (P 1 -P 2 ) / L is less than 50 MPa / m, where P 2 is an outflow pressure from the porous body, Is provided.
- the mixed gas source may cause the mixed gas to flow into the porous body under a condition that the pressure gradient is 30 MPa / m or less.
- the mixed gas may flow into the porous body under a temperature environment of room temperature.
- the mixed gas may flow into the porous body in a temperature environment heated to 200 ° C. or higher by the heating means.
- the mixed gas source may cause the mixed gas to flow into the porous body under a condition that the pressure gradient is 7.5 MPa / m or less, or 10 MPa / m or more.
- the pore diameter (D80) at which the number integration frequency in the cumulative pore diameter distribution of the porous body becomes 80% may be 800 nm or less.
- the porous body may be made of ceramics.
- the ceramics may be made of one or more inorganic materials selected from alumina materials, yttria-stabilized zirconia materials, and silicon carbide materials.
- the method for producing hydrogen gas according to the second aspect of the present invention comprises: Preparing a mixed gas containing carbon dioxide gas and hydrogen gas; Hydrogen gas and carbon dioxide gas can pass through the mixed gas, and the porous body in a direction in which the mixed gas permeates into a porous body that has a property of allowing hydrogen gas to permeate more easily than carbon dioxide gas.
- the hydrogen gas concentrating function of the porous body can be sufficiently exhibited by flowing the mixed gas into the porous body under the condition that the pressure gradient is less than 50 MPa / m.
- gas is introduced from one end surface of the porous body 100.
- the introduced gas passes through the porous body 100 and flows out from the other end surface of the porous body 100.
- the porous body 100 is a collection of thin tubes 100a.
- the mean free path of gas is ⁇ , and the diameter of each capillary 100a is 2r.
- a gas flux (hereinafter referred to as a permeate gas flux) J (P) passing through the porous body 100 is given by the following equation.
- the permeate gas flux represents the amount of gas passing through the unit cross section per unit time, and has a dimension of mol / (sec ⁇ m 2 ).
- ⁇ is the porosity of the porous body
- R is the gas constant
- T is the absolute temperature
- ⁇ is the viscosity of the gas
- L is the length of the porous body 100 in the permeating direction.
- ⁇ P P 1 ⁇ P 2
- P 1 is a gas inflow pressure into the porous body 100
- P 2 is a gas outflow pressure from the porous body 100.
- P E (P 1 + P 2 ) / 2.
- a physical quantity represented by ⁇ P / L is referred to as a pressure gradient.
- the permeate gas flux is theoretically proportional to the pressure gradient ⁇ P / L.
- the permeate gas flux is considered to be proportional to the pressure gradient ⁇ P / L.
- a graph with the pressure gradient ⁇ P / L on the x-axis and the permeate gas flux on the y-axis is represented by a straight line passing through the origin.
- the slope of the straight line specifically, the value of the proportionality coefficient multiplied by ⁇ P / L on the right side of the formula (1) or (2) varies depending on the gas type.
- the proportionality factor of hydrogen gas is larger than that of carbon dioxide gas. That is, the porous body 100 has a property that allows hydrogen gas to permeate more easily than carbon dioxide gas. For this reason, concentration of hydrogen gas is realizable when mixed gas of hydrogen gas and carbon dioxide gas is used as gas.
- the hydrogen gas concentration function of the porous body 100 can be evaluated by the ratio of the hydrogen gas flux to the gas flux flowing out of the porous body 100 (hereinafter referred to as the separation factor).
- the separation factor does not depend on the pressure gradient ⁇ P / L in both the Poiseuille flow and the Knudsen flow.
- the separation factor does not depend on the pressure gradient ⁇ P / L.
- Patent Document 1 in order to efficiently concentrate hydrogen gas, as shown in Patent Document 1, the porous body 100 has been used under a pressure gradient as high as possible.
- the porous body 100 can exhibit characteristics different from the technical common sense theoretically indicated by the formulas (1) and (2).
- main points among the found matters will be described with reference to FIG.
- FIG. 2 is a graph schematically showing the relationship between the permeate gas flux J and the pressure gradient ⁇ P / L.
- the x-axis indicates the pressure gradient ⁇ P / L, and the y-axis indicates the permeate gas flux J.
- the permeate gas flux J of hydrogen gas is represented by a straight line that passes through the origin as indicated by the straight line a-1 or a straight line having a y-axis intercept as shown by the straight line a-2. (Paper J. Asian. Ceram. Soc., 1, 368-373 (2013)).
- the permeate gas flux J of carbon dioxide gas is represented by a straight line having an x-axis intercept C without passing through the origin, as indicated by a straight line b. That is, the carbon dioxide gas does not permeate the porous body 100 until the pressure gradient ⁇ P / L reaches a certain critical value (hereinafter referred to as critical pressure gradient) C.
- the inventors of the present invention have measured the gradient of the permeate gas flux J between hydrogen gas and carbon dioxide gas under a low pressure gradient near or below the critical pressure gradient C.
- the idea that hydrogen gas can be concentrated by utilizing not only the difference but also the difference in the x-axis intercept was obtained.
- the present invention has been made based on such knowledge.
- Examples 1 to 3 Reference Examples 1 and 2
- a pH 3 dispersant is added and stirred for 24 hours.
- the dispersing agent liquid forms an electrostatic double layer on each particle of the ⁇ -alumina powder, thereby causing electrostatic repulsion between the particles.
- ⁇ -alumina powder accounts for 30 vol%, and the remainder is occupied by the dispersant solution.
- the suspension was filtered with an upper dehydrating filter to form a molded body. Further, the molded body was dried in air at 100 ° C. for 24 hours and then calcined in air at 800 ° C. for 1 hour to obtain an alumina porous body.
- FIG. 3A shows a scanning electron microscope (SEM) photograph of the obtained alumina porous body. As shown in the figure, a porous structure formed by adhering the ⁇ -alumina powder particles was confirmed.
- FIG. 3B shows the cumulative pore size distribution of the obtained alumina porous body.
- the pore size distribution of the porous body was measured by an intercept method using an SEM image.
- the maximum pore diameter was 150 nm, and the median diameter (D50) was 32 nm.
- the relative density refers to the ratio of the solid portion excluding pores in the total volume.
- room temperature refers to a temperature exceeding 0 ° C. and lower than 40 ° C.
- the hydrogen gas production apparatus has a porous body 100, an inflow port 200a at one end, an outflow port 200b at the other end, and a gas flow path in which the porous body 100 is disposed. 200 and a mixed gas source 300 that supplies a mixed gas from an inlet 200 a of the gas flow path 200.
- the porous body 100 is a substantially disk having a surface having an inflow region 101 into which a mixed gas supplied from a mixed gas source 300 flows, a back surface having an outflow region 102 through which gas flows out, and a side surface 103 connecting the front surface and the back surface. It is formed in a shape.
- the inflow region 101 is located approximately at the center of the front surface, and the outflow region 102 is located approximately at the center of the back surface.
- the porous body 100 has a gas leakage prevention film 104 on the peripheral edge except the inflow region 101 on the front surface, the peripheral edge except the outflow region 102 on the back surface, and the side surface 103 over the entire periphery.
- the gas leakage prevention film 104 is formed by applying a resin, specifically, a phenol resin.
- the gas flow path 200 includes a jig 210 that sandwiches the peripheral edge where the gas leakage prevention film 104 of the porous body 100 is formed from both sides in the thickness direction, and a holding member 220 that holds the jig 210.
- the jig 210 includes a ring-shaped sealing material 211 that is in contact with the gas leakage prevention film 104 on the surface of the porous body 100, a ring-shaped spacer 212 disposed on the sealing material 211, and a ring-shaped material disposed on the spacer 212. And a sealing material 213.
- the jig 210 is arranged on the ring-shaped sealing material 214 in contact with the gas leakage prevention film 104 on the back surface of the porous body 100, the ring-shaped spacer 215 disposed on the sealing material 214, and the spacer 215. And a ring-shaped sealing material 216.
- the sealing materials 211, 213, 214, and 216 are made of rubber.
- the spacers 212 and 215 are made of metal, specifically, stainless steel.
- a projection region obtained by projecting the sealing material 211, the spacer 212, and the sealing material 213 onto the surface of the porous body 100 substantially overlaps the region on the surface of the porous body 100 where the gas leakage prevention film 104 is formed. Further, the projection region obtained by projecting the sealing material 214, the spacer 215, and the sealing material 216 onto the back surface of the porous body 100 is substantially the same as the region where the gas leakage prevention film 104 is formed on the back surface of the porous body 100. Overlap.
- the holding member 220 includes a male member 221 and a female member 222 that sandwich the porous body 100 and the jig 210 in the thickness direction of the porous body 100.
- the male member 221 is in contact with the sealing material 213 and constitutes an inflow port 200a.
- the female member 222 is in contact with the sealing material 216 and constitutes the inflow port 200b.
- the male member 221 and the female member 222 are screwed together. By screwing one of the male member 221 and the female member 222 with respect to the other, one can be advanced or retracted in the thickness direction of the porous body 100 with respect to the other. Thereby, the pressure which airtightly clamps the jig 210 can be adjusted.
- the porous body 100 As the porous body 100, the above-mentioned alumina porous body is used, a mixed gas composed of hydrogen gas and carbon dioxide gas is supplied from the mixed gas source 300, and the porous body 100 is porous in a temperature environment of about 25 ° C. as room temperature.
- the hydrogen gas concentration ability of the body 100 was examined.
- the alumina porous body as the porous body 100, the gas flow path 200, and the mixed gas flowing into the porous body 100 are all at room temperature. It means a certain condition.
- the hydrogen gas concentration in the mixed gas supplied from the mixed gas source 300 was variously changed. Further, while maintaining the outflow pressure P 2 of the gas in the outflow region 102 of the porous body 100 to substantially atmospheric pressure (0.1 MPa), the inlet pressure P 1 of the gas mixture into the inlet region 101 of the porous body 100 By changing to various values, the pressure gradient ⁇ P / L was changed to various values.
- the length (thickness) L of the alumina porous body in the direction in which the mixed gas permeates is 3 mm.
- Q is the number of moles of gas permeated through the porous body 100, and was measured by gas chromatography.
- A is the area of the cross section perpendicular to the direction in which the gas of the porous body 100 permeates. This area is equal to the areas of the inflow region 101 and the outflow region 102.
- t is the time required for the gas to pass through the porous body 100.
- ⁇ is called a transmission coefficient.
- FIG. 5 shows a graph obtained by linearly approximating the plot of the measurement result of the permeate gas flux by the least square method.
- J (H 2 ) represents the permeated gas flux of hydrogen gas obtained from the above equation (3)
- J (CO 2 ) represents carbon dioxide gas obtained from the above equation (3).
- the horizontal axis common to each graph indicates the pressure gradient ⁇ P / L.
- the hydrogen gas concentration in the mixed gas supplied from the mixed gas source 300 was changed in three stages of 20 mol% (Example 1), 50 mol% (Example 2), and 80 mol% (Example 3).
- the permeate gas flux is also obtained for each of the case where the gas supplied from the mixed gas source 300 is 100 mol% of carbon dioxide gas (Reference Example 1) and the case of 100 mol% of hydrogen gas (Reference Example 2).
- the gas supplied from the mixed gas source 300 is 100 mol% of carbon dioxide gas (Reference Example 1) and the case of 100 mol% of hydrogen gas (Reference Example 2).
- the vertical scale is different between the upper graph and the lower graph.
- the slope of the upper graph that is, the permeability coefficient of hydrogen gas (see Equation (3)) is the slope of the lower graph, that is, the permeability coefficient of carbon dioxide gas (see Equation (3)). Bigger than).
- the graph of Reference Example 1 corresponds to the straight line b in FIG. 2, and the graph of Reference Example 2 corresponds to the straight line a-1 in FIG. Strictly speaking, not only the graph of Reference Example 1 but also the graph of Reference Example 2 has a non-zero x-axis intercept. However, a clear difference is recognized between the x-axis intercept of the graph of Reference Example 1 and the x-axis intercept of the graph of Reference Example 2.
- the critical pressure gradient difference was 5.6 MPa / m in Example 1, 4.4 MPa / m in Example 2, and 2.8 MPa / m in Example 3.
- the separation factor F (H 2 ) is an index for evaluating the hydrogen gas concentration capability of the porous body 100.
- FIG. 6 shows a graph in which the measurement results of the separation factor F (H 2 ) are plotted.
- the upper graph shows the results when the hydrogen gas concentration in the mixed gas supplied by the mixed gas source 300 is 80 mol% (Example 3), and the middle graph shows the results when the hydrogen gas concentration is 50 mol% (Example).
- the results of 2) are shown, and the lower graph shows the results when the hydrogen gas concentration is 20 mol% (Example 1).
- the horizontal axis common to each graph indicates the pressure gradient ⁇ P / L.
- FIG. 6 also shows the results of Examples 4 to 9 to be described later, and FIG. 6 will be referred to again in the description of Examples 4 to 9 later.
- separation factor F (H 2) is the pressure gradient [Delta] P / L should not depend. However, as shown in the figure, in any of Examples 1 to 3, the smaller the pressure gradient ⁇ P / L, the larger the separation factor F (H 2 ).
- the existence of the critical pressure gradient difference is considered as one of the main factors that brought about such a result. That is, when the critical pressure gradient difference exists, the pressure gradient ⁇ P / L is not canceled when the ratio of the permeate gas flux is taken as shown in the equation (4).
- the effect that the separation factor F (H 2 ) increases as the pressure gradient ⁇ P / L decreases is confirmed in a region where the pressure gradient ⁇ P / L is less than 50 MPa / m.
- the separation factor F (H 2 ) converges to a certain value as the pressure gradient ⁇ P / L increases.
- the separation factor F (H 2 ) As shown, it was observed that the pressure gradient ⁇ P / L became almost independent.
- Yttria-Stabilized Zirconia (YSZ) powder manufactured by Tosoh Corporation, product name: TZ-8Y having a specific surface area of 14.9 m 2 / g, a median diameter of 40 nm, and an isoelectric point of pH 7.8.
- Dispersant liquid was added and stirred for 24 hours to obtain a suspension.
- a dispersing agent liquid expresses an electrostatic repulsion force between particles by forming an electric double layer in each particle of YSZ powder.
- YSZ powder occupies 30 vol%, and the balance is the dispersant solution.
- the suspension was filtered with an upper dehydrating filter to form a molded body. Further, the molded body was dried in air at 100 ° C. for 24 hours and then fired in air at 1100 ° C. for 1 hour to obtain a YSZ porous body.
- the length (thickness) L of the YSZ porous body in the direction in which the mixed gas permeates is 3 mm.
- FIG. 7A shows an SEM photograph of the obtained YSZ porous material. As shown in the figure, a porous structure formed by adhering the particles of the YSZ powder was confirmed.
- FIG. 7B shows the cumulative pore size distribution of the obtained YSZ porous material.
- the pore size distribution of the porous body was measured by an intercept method using an SEM image.
- the maximum pore diameter was 190 nm, and the median diameter (D50) was 25 nm.
- the relative density was 50.4%
- the open porosity was 40.5%
- the closed porosity was 9.1%.
- FIG. 8 shows a graph obtained by linearly approximating the plot of the measurement result of the permeate gas flux by the least square method.
- the hydrogen gas concentration in the mixed gas supplied from the mixed gas source 300 was changed in three stages of 20 mol% (Example 4), 50 mol% (Example 5), and 80 mol% (Example 6).
- the permeate gas flux was also measured when the gas supplied from the mixed gas source 300 was 100 mol% carbon dioxide gas (Reference Example 3) and when the gas was 100 mol% hydrogen gas (Reference Example 4).
- the scale of the vertical axis is different between the upper graph and the lower graph in FIG.
- the slope of the upper graph that is, the permeability coefficient of hydrogen gas (see Equation (3)) is greater than the slope of the lower graph, that is, the permeability coefficient of carbon dioxide gas (see Equation (3)). large.
- the critical pressure gradient difference was 3.8 MPa / m in Example 4, 2.5 MPa / m in Example 5, and 2.1 MPa / m in Example 6.
- FIG. 6 also shows a graph in which the measurement results of the separation factor F (H 2 ) for Examples 4 to 6 are plotted.
- the pressure gradient ⁇ P / L is less than 50 MPa / m, the smaller the pressure gradient ⁇ P / L, the greater the separation factor F (H 2 ).
- the hydrogen gas concentration capability of the porous body 100 can be fully exerted.
- a separation factor higher than the theoretical value can be expressed.
- the pressure gradient ⁇ P / L is 30 MPa / m or less, the dependency of the separation factor F (H 2 ) on the pressure gradient ⁇ P / L increases, and the separation factor F (H 2 ) takes a large value.
- a joined body of the alumina porous body according to Examples 1 to 3 and the YSZ porous body according to Examples 4 to 6 (hereinafter referred to as alumina-YSZ bilayer porous body) was formed. Both the alumina porous body and the YSZ porous body had a thickness of 1.5 mm, and an alumina-YSZ bilayer porous body having a thickness of 3 mm was obtained.
- the alumina-YSZ bilayer porous body is used as the porous body 100 of the hydrogen gas production apparatus in FIG. 4, and hydrogen gas is used at room temperature of about 25 ° C. Was concentrated.
- the alumina-YSZ bilayer porous body was installed in the direction in which the mixed gas flows from the alumina porous body side. And the permeated gas flux of hydrogen gas and carbon dioxide gas was measured.
- FIG. 9 is a graph obtained by linearly approximating the plot of the measurement result of the permeate gas flux by the least square method.
- the hydrogen gas concentration in the mixed gas supplied from the mixed gas source 300 was changed in three stages of 20 mol% (Example 7), 50 mol% (Example 8), and 80 mol% (Example 9).
- the permeate gas flux was also measured when the gas supplied from the mixed gas source 300 was 100 mol% carbon dioxide gas (Reference Example 5) and when the gas was 100 mol% hydrogen gas (Reference Example 6).
- the scale of the vertical axis is different between the upper graph and the lower graph in FIG.
- the slope of the upper graph that is, the hydrogen gas permeability coefficient (see Equation (3)) is larger than the slope of the lower graph, ie, the carbon dioxide gas permeability coefficient (see Equation (3)). large.
- the critical pressure gradient difference was 4.7 MPa / m in Example 7, 2.6 MPa / m in Example 8, and 2.4 MPa / m in Example 9.
- FIG. 6 also shows a graph in which the measurement results of the separation factor F (H 2 ) for Examples 7 to 9 are plotted.
- the pressure gradient ⁇ P / L is less than 50 MPa / m
- the smaller the pressure gradient ⁇ P / L the larger the separation factor F (H 2 ).
- the pressure gradient ⁇ P / L is set to less than 50 MPa / m under a temperature environment of room temperature, the hydrogen gas concentration capability of the porous body 100 can be fully exerted.
- a separation factor higher than the theoretical value can be expressed.
- the pressure gradient ⁇ P / L is 30 MPa / m or less, the dependence of the separation factor F (H 2 ) on the pressure gradient ⁇ P / L increases, and the separation factor F (H 2 ) approaches 1.
- SiC silicon carbide
- the ⁇ -alumina powder used in Examples 1 to 3 was used as a sintering aid for the outer coating of 2 mass%, and the Y 2 O 3 purity exceeded 99.9 mass%.
- a Y 2 O 3 powder (manufactured by Shin-Etsu Chemical Co., Ltd.) having a surface area of 15.0 m 2 / g, a median diameter of 290 nm, and an isoelectric point of pH 7.5 was externally added and added in 2 mass% to obtain a mixed powder.
- a dispersant solution was added to and mixed with the obtained mixed powder to obtain a suspension with a solid content of 30 vol% and a pH of 5.
- the suspension was stirred for 24 hours and then solidified on a gypsum plate to obtain a solidified product. Furthermore, the obtained solidified product was pressure-sintered at 39 MPa for 2 hours in an Ar atmosphere to obtain a silicon carbide based porous material.
- 10A to 10C show SEM photographs of the obtained silicon carbide based porous material.
- 10A shows what was sintered at 1400 ° C.
- FIG. 10B shows what was sintered at 1500 ° C.
- FIG. 10C shows what was sintered at 1700 ° C.
- a porous structure formed by fixing the particles of the silicon carbide powder was confirmed.
- FIG. 11 shows the cumulative pore size distribution of the obtained silicon carbide based porous material.
- the pore size distribution of the porous body was measured by an intercept method using an SEM image.
- the median diameter (D50) of the silicon carbide based porous material was 48 nm when sintered at 1400 ° C., 112 nm when sintered at 1500 ° C., and 152 nm when sintered at 1700 ° C. Further, the maximum pore diameter of the sintered product at 1700 ° C. was about 3000 nm.
- the pore diameter (D80) of the silicon carbide based porous material sintered at any temperature of 1400 ° C., 1500 ° C., and 1700 ° C. has a number integration frequency of 80% in the cumulative pore diameter distribution. It was 800 nm or less.
- the relative density of the silicon carbide based porous material having a sintering temperature of 1400 ° C. was 61.1%, the open porosity was 36.1%, The closed porosity was 2.8%.
- the relative density of the porous silicon carbide body with a sintering temperature of 1500 ° C. was 69.3%, the open porosity was 28.1%, and the closed porosity was 2.6%.
- the relative density of the silicon carbide porous material having a sintering temperature of 1700 ° C. was 75.4%, the open porosity was 17.9%, and the closed porosity was 6.7%.
- the above three types of silicon carbide porous bodies were used as the porous body 100 of the hydrogen gas production apparatus of FIG. Then, hydrogen gas was concentrated.
- the hydrogen gas concentration in the mixed gas supplied from the mixed gas source 300 was changed in three stages of 20 mol%, 50 mol%, and 80 mol%.
- Table 1 shows the relationship between the example numbers and the experimental conditions.
- the critical pressure gradient difference is 0.3 MPa / m in Example 10, 1.1 MPa / m in Example 11, 1.0 MPa / m in Example 12, 0.3 MPa / m in Example 13, and in Example 14.
- Example 15 was 2.3 MPa / m
- Example 16 was 0.7 MPa / m
- Example 17 was 0.6 MPa / m
- Example 18 was 1.6 MPa / m.
- FIG. 12 shows a graph plotting the measurement results of the separation factor F (H 2 ).
- the separation factor F (H 2 ) increases as the pressure gradient ⁇ P / L decreases in a region where the pressure gradient ⁇ P / L is less than 25 MPa / m in a temperature environment at room temperature. The result was seen. In particular, when the pressure gradient ⁇ P / L is 10 MPa / m or less, the dependency of the separation factor F (H 2 ) on the pressure gradient ⁇ P / L increases, and the separation factor F (H 2 ) approaches 1.
- FIG. 13 shows a schematic partial sectional view of a hydrogen gas production apparatus used for hydrogen gas concentration.
- This hydrogen gas production apparatus includes a porous body 400, a gas flow channel 500 in which the porous body 400 is disposed, a mixed gas source 600 that supplies a mixed gas from an inlet 500a of the gas flow channel 500, a gas And an inert gas source 700 for supplying argon gas as an inert gas from the outlet 500b of the channel 500.
- the porous body 400 has a surface having an inflow region 401 through which mixed gas flows, a back surface having an outflow region 402 through which gas flows out, and a side surface 403 connecting the front and back surfaces.
- the front surface and the back surface face each other in the thickness direction of the porous body 400.
- the gas flow channel 500 holds the porous body 400 in a state in which the peripheral portion of the porous body 400 that is circular in plan view is sandwiched in the thickness direction and the side surface 403 of the porous body 400 is hermetically surrounded.
- the first holding member 510 and the second holding member 520 sandwiching the first holding member 510 in a direction parallel to the thickness direction of the porous body 400 are configured.
- the first holding member 510 sandwiches the porous body 400 via metal annular sealing materials 531 and 532.
- the first holding member 510 includes a male member 511 and a female member 512 that are screwed together.
- One of the male member 511 and the female member 512 can be advanced and retracted in the thickness direction of the porous body 400 by screwing it with respect to the other. Thereby, the pressure which pinches
- the second holding member 520 sandwiches the first holding member 510 via metal annular seal materials 541 and 542.
- the second holding member 520 is also composed of a male member 521 and a female member 522 that are screwed together, and the thickness of the porous body 400 can be increased by screwing one of the male member 521 and the female member 522 relative to the other. It can be moved forward and backward. Thereby, the pressure which pinches
- the female member 522 constitutes the inflow port 500a of the gas flow path 500, and has a double tube structure including an inner tube 522a and an outer tube 522b.
- the mixed gas source 600 allows the mixed gas to flow from the inner tube 522a.
- a valve 522c is interposed between the inner tube 522a and the outer tube 522b.
- the male member 521 constitutes the outlet 500b of the gas flow channel 500, and has a double tube structure composed of an inner tube 521a and an outer tube 521b, similar to the female member 522.
- the inert gas source 700 allows argon gas to flow from the inner tube 521a.
- the gas that has passed through the porous body 400 flows out between the inner tube 521a and the outer tube 521b together with the argon gas.
- the hydrogen gas production apparatus described above is installed inside an electric furnace 800 as a heating means.
- Hydrogen gas was concentrated in a temperature environment in which the environmental temperature in the electric furnace 800 was stabilized at 200 ° C, 400 ° C, or 500 ° C.
- stabilizing the environmental temperature in the electric furnace 800 at T ° C. means a condition where the porous body 400 and the gas flow path 500 are stabilized at T ° C.
- the mixed gas is also heated by the gas flow channel 500 in the process of flowing through the gas flow channel 500 and is brought close to T ° C.
- the pressure gradient ⁇ P / L was variously changed.
- the length (thickness) L of the porous body 400 in the direction in which the mixed gas permeates is 3 mm.
- the permeate gas flow rate defined by the above equation (3) was measured with a soap film flow meter for each of hydrogen gas and carbon dioxide gas.
- argon gas was supplied from an inert gas source 700 at a pressure of 0.1 MPa (atmospheric pressure) and a flow rate of about 5 ml / min.
- a permeated gas having a small flux it was possible to collect a permeated gas having a small flux. That is, even a permeate gas having a small flux can flow out from between the inner tube 521a and the outer tube 521b together with the argon gas without being retained in the gas flow path 500, and can be used for the measurement of the permeate gas flow rate. it can.
- the hydrogen gas concentration in the mixed gas supplied from the mixed gas source 600 was changed in three stages of 20 mol%, 50 mol%, and 80 mol%. During the transition period in which the hydrogen gas concentration is changed, the valve 522c is opened to allow the mixed gas to flow out from the inlet 500a. As a result, the influence of this transient period is less likely to appear in the measurement result of the permeate gas flux. Hydrogen gas concentration in the mixed gas is in a stable stage, closing the valve 522c, enhanced inflow pressure P 1 of the gas mixture into the porous body 400.
- the porous body 400 is a molded body obtained by filtering a suspension composed of ⁇ -alumina powder 30 vol% and the remaining dispersant solution in the same manner as in Examples 1 to 3 described above. A sintered product was used. However, hydrogen gas was concentrated using two types of porous bodies 400, one having a sintering temperature of 900 ° C. and one having 1100 ° C.
- the density of the porous body 400 varies depending on the sintering temperature.
- the relative density, open porosity, and closed porosity of the alumina porous body sintered at 900 ° C. were 59.3%, 40.4%, and 0.3%, respectively.
- the relative density, open porosity, and closed porosity of the alumina porous body sintered at 1100 ° C. were 70.2%, 29.3%, and 0.5%, respectively.
- Table 2 shows the relationship between the example numbers and the experimental conditions.
- FIG. 14 is a graph plotting the measurement results of the permeate gas flux according to Examples 19 to 26.
- J (H 2 ) represents the permeate flux of hydrogen gas obtained from the above equation (3)
- J (CO 2 ) represents carbon dioxide obtained from the above equation (3).
- the horizontal axis common to each graph indicates the pressure gradient ⁇ P / L.
- the permeate gas flow rate of either hydrogen gas or carbon dioxide gas did not show a critical pressure gradient that is an intercept with respect to the horizontal axis. Further, in both hydrogen gas and carbon dioxide gas, the permeate gas flux decreased as the environmental temperature, that is, the temperature in the electric furnace increased.
- Example 21 As shown in the upper J (H 2 ) graph, in Example 21, the hydrogen gas permeation flux increased with an increase in pressure gradient and then decreased slightly. Further, as shown in the lower graph of J (CO 2 ), in Examples 20 and 21, the carbon dioxide gas permeation flux decreases with an increase in the pressure gradient, and the pressure gradient is 28 Mpa / m or more and 1 mmol. / S / m 2 or less.
- FIG. 15 is a graph plotting the measurement results of the separation factor F (H 2 ) defined by the above equation (4) for Examples 19 to 26.
- the upper graph shows the results when the hydrogen gas concentration in the mixed gas supplied by the mixed gas source 600 is 80 mol% (Examples 19 to 21), and the middle graph shows the hydrogen gas concentration of 50 mol%.
- the results in the cases (Examples 22 to 24) are shown, and the lower graph shows the results when the hydrogen gas concentration is 20 mol% (Examples 25 and 26).
- the horizontal axis common to each graph indicates the pressure gradient ⁇ P / L.
- FIG. 16 shows a graph in which the measurement results of the permeate gas flux according to Examples 27 to 32 are plotted. Similar to the results shown in FIG. 14, the permeate gas flow rates of hydrogen gas and carbon dioxide gas did not show a critical pressure gradient that is an intercept with respect to the horizontal axis. Further, in both the hydrogen gas and the carbon dioxide gas, the fluctuations of the permeate gas flux showed almost the same tendency at the environmental temperatures of 200 ° C. and 400 ° C. That is, for both hydrogen gas and carbon dioxide gas, the permeate gas flux increased as the pressure gradient increased.
- FIG. 17 shows a graph in which the measurement results of the hydrogen gas separation factor F (H 2 ) for Examples 27 to 32 are plotted.
- the upper graph shows the results when the hydrogen gas concentration in the mixed gas supplied by the mixed gas source 600 is 80 mol% (Examples 27 and 28), and the interruption graph shows the hydrogen gas concentration is 50 mol%.
- the results in the cases (Examples 29 and 30) are shown, and the lower graph shows the results when the hydrogen gas concentration is 20 mol% (Examples 31 and 32).
- the horizontal axis common to each graph indicates the pressure gradient ⁇ P / L.
- FIG. 18 plots the separation coefficient F (H 2 ) shown in FIG. 15 and FIG. 17 on the same graph, and approximates the variation of the plot with a curve.
- the upper graph shows the results when the hydrogen gas concentration in the mixed gas supplied by the mixed gas source 600 is 80 mol%
- the interruption graph shows the results when the hydrogen gas concentration is 50 mol%.
- These graphs show the results when the hydrogen gas concentration is 20 mol%.
- the horizontal axis common to each graph indicates the pressure gradient ⁇ P / L.
- the separation factor F (H 2 ) tends to increase as the pressure gradient decreases. That is, as in the case of a room temperature environment (see FIGS. 6 and 12), a better separation factor F (H 2 ) is obtained in a region where the pressure gradient is lower. From this, it was found that when the pressure gradient is limited to a low level, the effect of sufficiently exerting the hydrogen gas condensing function of the porous body does not depend on the environmental temperature.
- the separation factor F (H 2 ) tends to increase as the pressure gradient increases. That is, in this region, the greater the pressure gradient, the better the separation factor F (H 2 ).
- This tendency is a phenomenon peculiar to a high temperature environment of 200 ° C. or higher, which is not seen in the experimental results at room temperature (see FIGS. 6 and 12).
- the hydrogen gas concentration function of the porous body can be sufficiently exerted, and a good separation factor F (H 2 ) can be obtained. Therefore, hydrogen gas can be concentrated efficiently. Therefore, it can be said that it is particularly desirable to concentrate hydrogen gas at a high temperature from the viewpoint of industrial use.
- the hydrogen gas concentration in the mixed gas is preferably 50 mol% or more, and more preferably 80 mol% or more.
- hydrogen gas concentration in a temperature environment of 200 ° C. or higher is realized by heating the gas flow path 500 and the porous body 400 by the electric furnace 800 as a heating means.
- the gas flow channel 500 and the porous body 400 are not directly heated, but the mixed gas is heated by the heating means, thereby realizing the concentration of hydrogen gas in a temperature environment of 200 ° C. or higher.
- the material of the porous body is not particularly limited.
- the porous body may be formed of an inorganic material or an organic material.
- the porous body is preferably formed of an inorganic material such as an inorganic compound, a metal, or a semiconductor, and in particular, formed of a ceramic that is a sintered body obtained by baking and solidifying an inorganic material. More preferred.
- the inorganic material forming the ceramic include the alumina material, yttria-stabilized zirconia material, and silicon carbide material used in the above examples, for example, siliceous material, boron material, magnesium oxide material, calcium oxide.
- phase-separated glass can be used as the ceramic.
- the pore size distribution of the porous body is not particularly limited as long as the porous body is permeable to hydrogen gas and carbon dioxide gas and has a property of allowing hydrogen gas to permeate more easily than carbon dioxide gas.
- the porous body does not concentrate hydrogen gas only by a so-called molecular sieving function.
- the molecular sieving function means that only hydrogen gas is allowed to pass through pores larger than the molecular diameter of hydrogen molecules and smaller than the molecular diameter of carbon dioxide molecules, for example, pores having a diameter of about 0.35 nm. The function to prevent.
- the porous material used in each of the above examples can permeate both hydrogen gas and carbon dioxide gas, it is inherent to molecules such as a difference in molecular diameter and a difference in average velocity between hydrogen molecules and carbon dioxide molecules. Because of this property, it has the property of allowing hydrogen gas to permeate more easily than carbon dioxide gas.
- the porous body when the pore diameter of the porous body is as large as, for example, about 10 mm, the porous body cannot have the property of allowing hydrogen gas to permeate more easily than carbon dioxide gas.
- the porous body when D80 is 800 nm or less and when D50 is 400 nm or less, the porous body can have the property of allowing hydrogen gas to permeate more easily than carbon dioxide gas. It was confirmed.
- Outlet 510 ... First holding member, 511 ... Male member, 512 ... Female member, 520 ... Second holding member, 521 ... Male member, 521a ... inner tube, 521b ... outer tube, 522 ... female member, 522a ... inner tube, 522b ... outer tube, 522c ... valve, 531,532,541,542 ... annular Lumpur material, 600 ... source of mixing gas, 700 ... inert gas source, 800 ... electric furnace (heating means).
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Abstract
Description
CmHn+2mH2O→(2m+n/2)H2+mCO2
水素ガス及び二酸化炭素ガスが透過可能であると共に、水素ガスを二酸化炭素ガスよりも透過させやすい性質をもつ多孔質体と、
前記多孔質体に、二酸化炭素ガス及び水素ガスを含む混合ガスを、該混合ガスが透過する方向の前記多孔質体の長さをL、該混合ガスの前記多孔質体への流入圧力をP1、前記多孔質体からの流出圧力をP2としたとき、(P1-P2)/Lで表される圧力勾配が50MPa/m未満となる条件で流入させる混合ガス源と、
を備える。
前記加熱手段によって200℃以上に加熱された温度環境下で、前記多孔質体に前記混合ガスが流入されてもよい。
二酸化炭素ガス及び水素ガスを含む混合ガスを準備する工程と、
前記混合ガスを、水素ガス及び二酸化炭素ガスが透過可能であると共に、水素ガスを二酸化炭素ガスよりも透過させやすい性質をもつ多孔質体に、該混合ガスが透過する方向の前記多孔質体の長さをL、該混合ガスの前記多孔質体への流入圧力をP1、前記多孔質体からの流出圧力をP2としたとき、(P1-P2)/Lで表される圧力勾配が50MPa/m未満となる条件で流入させる工程と、
を有する。
比表面積10.5m2/g、メディアン径310nm、等電点pH8.5のα-アルミナ粉体(住友化学社製、製品名:AKP50)に、pH3の分散剤液を加えて24時間攪拌し、サスペンションを得た。なお、分散剤液は、α-アルミナ粉体の各粒子に電気二重層を形成することで、粒子間に静電反発力を発現させる。サスペンションは、α-アルミナ粉体が30vol%を占め、残部を分散剤溶液が占める。
次に、実施例4~6、参考例3及び4について述べる。
次に、実施例7~9、参考例5及び6について述べる。
次に、実施例10~18について述べる。
Claims (9)
- 水素ガス及び二酸化炭素ガスが透過可能であると共に、水素ガスを二酸化炭素ガスよりも透過させやすい性質をもつ多孔質体と、
前記多孔質体に、二酸化炭素ガス及び水素ガスを含む混合ガスを、該混合ガスが透過する方向の前記多孔質体の長さをL、該混合ガスの前記多孔質体への流入圧力をP1、前記多孔質体からの流出圧力をP2としたとき、(P1-P2)/Lで表される圧力勾配が50MPa/m未満となる条件で流入させる混合ガス源と、
を備える水素ガス製造装置。 - 前記混合ガス源が、前記圧力勾配が30MPa/m以下となる条件で、前記多孔質体に前記混合ガスを流入させる請求項1に記載の水素ガス製造装置。
- 室温の温度環境下で、前記多孔質体に前記混合ガスが流入される請求項1又は2に記載の水素ガス製造装置。
- 前記多孔質体と前記混合ガスの少なくともいずれかを加熱する加熱手段をさらに備え、
前記加熱手段によって200℃以上に加熱された温度環境下で、前記多孔質体に前記混合ガスが流入される請求項1又は2に記載の水素ガス製造装置。 - 前記混合ガス源が、前記圧力勾配が7.5MPa/m以下、又は10MPa/m以上となる条件で、前記多孔質体に前記混合ガスを流入させる請求項4に記載の水素ガス製造装置。
- 前記多孔質体の累積細孔径分布における個数積算頻度が80%となる点の細孔直径(D80)が、800nm以下である請求項1から5のいずれか1項に記載の水素ガス製造装置。
- 前記多孔質体が、セラミックスよりなる請求項1から6のいずれか1項に記載の水素ガス製造装置。
- 前記セラミックスが、アルミナ質材料、イットリア安定化ジルコニア質材料、及び炭化珪素質材料から選ばれる1種以上の無機材料よりなる請求項7に記載の水素ガス製造装置。
- 二酸化炭素ガス及び水素ガスを含む混合ガスを準備する工程と、
前記混合ガスを、水素ガス及び二酸化炭素ガスが透過可能であると共に、水素ガスを二酸化炭素ガスよりも透過させやすい性質をもつ多孔質体に、該混合ガスが透過する方向の前記多孔質体の長さをL、該混合ガスの前記多孔質体への流入圧力をP1、前記多孔質体からの流出圧力をP2としたとき、(P1-P2)/Lで表される圧力勾配が50MPa/m未満となる条件で流入させる工程と、
を有する水素ガス製造方法。
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KOTA GOTANDA ET AL.: "Separation of H2/CO2 mixed gas through porous alumina compact", THE 31ST INTERNATIONAL KOREA - JAPAN SEMINAR ON CERAMICS, 2014, pages 295, XP055349411 * |
Cited By (1)
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JP2021013902A (ja) * | 2019-07-12 | 2021-02-12 | 株式会社ハイドロネクスト | 水素分離装置及びその製造方法 |
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US10882005B2 (en) | 2021-01-05 |
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