A hydrogen purification device for desulfurization using a metal nano-mesoporous structure catalyst

Abstract

The present invention relates to a hydrogen purification device for desulfurization using a metal nano-mesoporous structure catalyst, comprising a reactor, a sieve plate assembly is arranged at the bottom of the inner cavity of the reactor, a metal nano-mesoporous structure catalyst is filled above the sieve plate assembly to form a packing layer, a gas phase inlet gas distributor is arranged above the packing layer; the gas phase inlet gas distributor has a disc, the disc is distributed with a certain number of gas distribution holes, the gas distribution holes include an upper opening and a lower opening, the lower opening is formed into a cone, the cone angle Q of the cross section of the lower opening is 15-30°, the gas phase flow rate of the lower opening plane through the lower opening is 0.15-0.2 m / s, the gas phase medium passing through the lower opening is decelerated and expanded, and the gas phase medium is prevented from generating wall flow or channel flow in the packing layer. The hydrogen purification device of the present invention is adopted to meet the requirements of the impurity sulfur content of hydrogen used in fuel cells.

Description

Technical Field

[0001] The invention relates to the technical field of hydrogen purification, in particular to a hydrogen purification device for desulfurization using a metal nano-mesoporous structure catalyst. Background Art

[0002] In recent years, with the rapid development of global hydrogen energy application technology, the application of hydrogen fuel cells has shown an industrial development trend, and the demand for hydrogen energy has increased significantly. No matter which method is used to prepare hydrogen, crude hydrogen is produced, and various impurities have a great impact on the application of hydrogen. Sulfides in hydrogen can have a destructive effect on the fuel cell system, affecting its life and working efficiency. The purity of hydrogen also requires a higher requirement. Therefore, the desulfurization of pure hydrogen is an indispensable and important link in the application of hydrogen. GB / T37244-2018 "Hydrogen for Proton Exchange Membrane Fuel Cell Vehicles" is the quality standard for hydrogen used in current fuel cell vehicles. This standard not only has requirements for hydrogen purity (≥99.97%), but also has extremely strict requirements for the impurity sulfur content, with an index of ≤0.004μmol / mol. The main content of high-purity hydrogen on the market is ≥99.999%, and some of it has been sold as hydrogen for fuel cells. However, there is no specific content index requirement for impurity sulfur in the standard GB / T3634.2-2011 "Hydrogen Part 2 High-purity Hydrogen". According to sampling analysis, the impurity sulfur content index of most high-purity hydrogen product gases is generally distributed in the range of 0.012 to 0.02μmol / mol. If the fuel cell vehicle stack uses high-purity hydrogen for a long time, it will cause irreversible damage and loss to the stack. Therefore, high-purity hydrogen cannot be directly used as hydrogen for fuel cells. It must be deeply desulfurized before use.

[0003] In summary, the existing fuel cell hydrogen desulfurization has the following problems:

[0004] First, the existing fuel cell desulfurization equipment cannot achieve deep desulfurization. The sulfur content in the fuel cell is difficult to reach below 0.004μmol / mol. The high sulfur content in the fuel cell will cause corrosion to the sulfide battery system, which will seriously endanger the life of the fuel cell.

[0005] The existing fuel cell desulfurization device has a complex process, requires multiple desulfurization processes, requires a large number of equipment, occupies a large area, and the acid gas generated needs to be further processed in a recovery device, which consumes a certain amount of financial resources. Summary of the invention

[0006] The technical problem to be solved by the present invention is to provide a hydrogen purification device for desulfurization using a metal nano-mesoporous structure catalyst, which is used for removing sulfur from hydrogen.

[0007] The technical solution adopted by the present invention to solve the above technical problems is: a hydrogen purification device using a metal nano-mesoporous structure catalyst for desulfurization, comprising a reactor, a sieve plate assembly is arranged at the bottom of the inner cavity of the reactor, a metal nano-mesoporous structure catalyst is filled above the sieve plate assembly to form a packing layer, and a gas phase inlet gas distributor is arranged above the packing layer; the gas phase medium input port of the reactor is located above the gas phase inlet gas distributor, and the gas phase medium output port of the reactor is located below the sieve plate assembly;

[0008] The gas phase inlet gas distributor has a disc, which is a disc-type steel structure. The disc is distributed with a certain number of gas distribution holes, and the gas distribution holes include an upper opening and a lower opening. The upper opening is straight, and the lower opening is formed into a cone. The cone angle Q of the cross section of the lower opening is 15 to 30 degrees. The gas phase flow rate of the lower plane through the lower opening is 0.15 to 0.2 m / s. The gas phase medium passing through the lower opening is decelerated and expanded, so that the gas phase medium forms a positive pressure difference through the gas phase inlet gas distributor, which compacts the packing layer and prevents the gas phase medium from generating wall flow or channel flow in the packing layer.

[0009] Preferably, the diameter d of the upper opening is 8-25 mm, the depth t of the upper opening is 20-50 mm, the distance s between the central axes of two adjacent upper openings is 50-80 mm, and the height h of the disc is 80-120 mm.

[0010] Preferably, the metal nano-mesoporous structure catalyst comprises molecular sieve-supported nano-scale metal Pt nanoparticles, the particle size of the molecular sieve-supported nano-scale metal Pt nanoparticles is 1-2 nm, and the Pt metal loading in the molecular sieve-supported nano-scale metal Pt nanoparticles is 1 wt%.

[0011] Preferably, the metal nano-mesoporous structure catalyst contains Ga, Na, Si, and Al; and the adsorption critical diameter of the metal nano-mesoporous structure catalyst is not greater than 4 nm.

[0012] Preferably, the sieve plate assembly consists of a metal filter, a sieve plate and a support frame. The sieve plate is supported by the support frame at the bottom of the reactor. The metal filter is installed on the sieve plate. The metal filter is made of stainless steel 316L, and the filter mesh number is 18 to 30.

[0013] Preferably, the hydrogen input pipeline is connected to the gas medium input port of the reactor through valve 1, and the hydrogen output pipeline is connected to the gas medium output port of the reactor through valve 2; the hydrogen before purification is input from the hydrogen input pipeline, and the content of gas-phase sulfur in the hydrogen before purification is ≤0.02 μmol / mol; the purified hydrogen is output from the hydrogen output pipeline, and the content of gas-phase sulfur in the hydrogen after purification is ≤0.004 μmol / mol.

[0014] Preferably, the gas pressure of the valve 1 is controlled by a pressure regulator PIC.

[0015] Preferably, a catalyst discharge port is provided on the side of the reactor corresponding to the packing layer.

[0016] Preferably, the reactor is provided with a temperature sensor PT for detecting the temperature of the upper portion of the packing layer and a temperature sensor TT for detecting the temperature of the lower portion of the packing layer.

[0017] The beneficial effect of the present invention is that the hydrogen purification device using the metal nano-mesoporous structure catalyst for desulfurization can remove sulfur from hydrogen, including both organic sulfur and inorganic sulfur. After being processed by the hydrogen purification device, purified hydrogen is output, thereby meeting the requirements for the impurity sulfur content of hydrogen used in fuel cells.

[0018] The gas distribution hole comprises an upper opening and a lower opening, wherein the upper opening is straight, and the lower opening is formed into a cone, and the cone angle Q of the cross section of the lower opening is 15 to 30 degrees, and the gas phase flow rate of the lower plane through the lower opening is 0.15 to 0.2 m / s. The gas phase medium passing through the lower opening is decelerated and expanded, so that a positive pressure difference is formed by the gas phase medium through the gas phase inlet gas distributor, which compacts the packing layer, prevents the gas phase medium from generating wall flow or channel flow in the packing layer, plays the role of a solid phase filler in a dense packing layer, and at the same time enhances the mass transfer effect between the gas and solid phases. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 It is a structural schematic diagram of the hydrogen purification device of the present invention;

[0020] Figure 2 is a schematic top view of a disc in a gas phase inlet gas distributor in the present invention;

[0021] Figure 3 is a partial cross-sectional schematic diagram of the disc in the present invention;

[0022] Wherein: 101, reactor; 102, gas phase inlet gas distributor; 103, packing layer; 104, sieve plate assembly; 105, catalyst outlet; 106, gas distribution hole; 201, valve one; 202, valve two; 301, hydrogen input pipeline; 302; hydrogen output pipeline. DETAILED DESCRIPTION

[0023] The present invention will now be described in further detail in conjunction with the accompanying drawings and preferred embodiments. These drawings are simplified schematic diagrams, which only illustrate the basic structure of the present invention in a schematic manner, and therefore only show the components related to the present invention.

[0024] like Figure 1 As shown, a hydrogen purification device for desulfurization using a metal nano-mesoporous structure catalyst comprises a reactor 101, a sieve plate assembly 104 is arranged at the bottom of the inner cavity of the reactor 101, a metal nano-mesoporous structure catalyst is filled above the sieve plate assembly 104 to form a packing layer 103, and a gas phase inlet gas distributor 102 is arranged above the packing layer 103; the gas phase medium input port of the reactor 101 is located above the gas phase inlet gas distributor 102, and the gas phase medium output port of the reactor 101 is located below the sieve plate assembly 104; specifically, in an optional embodiment, a catalyst discharge port 105 is arranged on the side of the reactor 101 corresponding to the packing layer 103. Specifically, in an optional embodiment, the reactor wall of the reactor 101 is made of 0Cr17Ni12Mo2 stainless steel.

[0025] like Figure 2 As shown, the gas phase inlet gas distributor 102 has a disc, which is a disc-shaped steel structure, and a certain number of gas distribution holes 106 are distributed on the disc. Figure 3 As shown, the gas distribution hole 106 includes an upper opening and a lower opening, the upper opening is straight, the lower opening is formed into a cone, the cone angle Q of the cross section of the lower opening is 15 to 30°, the diameter d of the upper opening is 8 to 25 mm, the depth t of the upper opening is 20 to 50 mm, the distance s between the central axes of two adjacent upper openings is 50 to 80 mm, and the height h of the disc is 80 to 120 mm. The gas phase flow rate at the lower plane of the lower opening is 0.15-0.2 m / s, which reduces the speed and expands the pressure of the gas phase medium passing through the lower opening, so that a positive pressure difference is formed through the gas phase inlet gas distributor 102, which compacts the packing layer 103 and prevents the gas phase medium from generating wall flow or channel flow in the packing layer 103, thereby compacting the solid phase filler in the packing layer 103 and enhancing the mass transfer effect between the gas and solid phases.

[0026] Specifically, in an optional embodiment, the metal nano-mesoporous structure catalyst includes molecular sieve-supported nano-scale metal Pt nanoparticles, the particle size of the molecular sieve-supported nano-scale metal Pt nanoparticles is 1-2nm, and the Pt metal loading in the molecular sieve-supported nano-scale metal Pt nanoparticles is 1wt%. The metal Pt nanoparticles have strong adsorption and binding energy for sulfur-containing gases.

[0027] Specifically, in an optional embodiment, the metal nano-mesoporous structure catalyst contains Ga, Na, Si, and Al; the adsorption critical diameter of the metal nano-mesoporous structure catalyst is not greater than 4 nm. Precious metals such as Ga, Na, Si, and Al are used to improve the activity of the catalyst.

[0028] Specifically, in an optional embodiment, the sieve plate assembly 104 is composed of a metal filter, a sieve plate and a support frame. The sieve plate is supported by the support frame at the bottom of the reactor 101. The metal filter is installed on the sieve plate. The material of the metal filter is stainless steel 316L, and the filter mesh number is 18 to 30.

[0029] Specifically, in an optional embodiment, the hydrogen input pipeline 301 is connected to the gas medium input port of the reactor 101 through the valve 1 201, and the hydrogen output pipeline 302 is connected to the gas medium output port of the reactor 101 through the valve 2 202; the hydrogen before purification is input from the hydrogen input pipeline 301, and the hydrogen before purification contains a gas-phase sulfur content of ≤0.02μmol / mol; the purified hydrogen is output from the hydrogen output pipeline 302, and the hydrogen after purification contains a gas-phase sulfur content of ≤0.004μmol / mol.

[0030] Specifically, in an optional embodiment, the gas pressure of the valve 201 is controlled by the pressure regulator PIC so that the pressure of the gas medium between the valve 201 and the gas medium input port of the reactor 101 is maintained at 1.8-2.0 MPa; the gas medium flow rate between the valve 201 and the gas medium input port of the reactor 101 is controlled by the valve 201.

[0031] Specifically, in an optional embodiment, the reactor 101 is provided with a temperature sensor PT for detecting the upper temperature of the packing layer 103 and a temperature sensor TT for detecting the lower temperature of the packing layer 103. The upper temperature of the packing layer 103 and the lower temperature of the packing layer 103 can be obtained through the temperature sensor PT and the temperature sensor TT, and the temperature of the packing layer 103 can be obtained in real time.

[0032] The hydrogen purification device for desulfurization using a metal nano-mesoporous structure catalyst of the present invention is used, the content of gas-phase sulfur in hydrogen before purification is ≤0.02 μmol / mol, and the purified hydrogen is output after being treated by the hydrogen purification device, and the content of gas-phase sulfur in the purified hydrogen is ≤0.004 μmol / mol, thereby meeting the requirement of fuel cell hydrogen for impurity sulfur content of ≤0.004 μmol / mol. The hydrogen purification process of the present invention is relatively simple, clean, and energy-saving, and the obtained hydrogen is suitable for fuel cells, semiconductor devices, precision instruments, etc.

[0033] The above description only describes the specific implementation mode of the present invention. Various examples do not limit the essential content of the present invention. After reading the description, ordinary technicians in the relevant technical field can modify or deform the specific implementation modes described above without departing from the essence and scope of the invention.

Claims

1. A hydrogen purification device for desulfurization using a metal nano-mesoporous catalyst, comprising a reactor (101), characterized in that: A sieve plate assembly (104) is arranged at the bottom of the inner cavity of the reactor (101); a metal nano-mesoporous structure catalyst is filled above the sieve plate assembly (104) to form a packing layer (103); a gas phase inlet gas distributor (102) is arranged above the packing layer (103); a gas phase medium input port of the reactor (101) is located above the gas phase inlet gas distributor (102); and a gas phase medium output port of the reactor (101) is located below the sieve plate assembly (104); The gas phase inlet gas distributor (102) has a disk, the disk is a disk-type steel structure, a certain number of gas distribution holes (106) are distributed on the disk, the gas distribution holes (106) include an upper opening and a lower opening, the upper opening is straight, the lower opening is formed in a cone, the cone angle Q of the cross section of the lower opening is 15 to 30 degrees, the gas phase flow rate through the lower opening plane of the lower opening is 0.15 to 0.2 m / s, the gas phase medium passing through the lower opening is decelerated and expanded, so that the gas phase medium forms a positive pressure difference through the gas phase inlet gas distributor (102), which has a compacting effect on the packing layer (103), and prevents the gas phase medium from generating wall flow or channel flow in the packing layer (103); The diameter d of the upper opening is 8 to 25 mm, the depth t of the upper opening is 20 to 50 mm, the distance s between the central axes of two adjacent upper openings is 50 to 80 mm, and the height h of the disc is 80 to 120 mm; The metal nano-mesoporous structure catalyst comprises molecular sieve-loaded nano-scale metal Pt nanoparticles, the particle size of the molecular sieve-loaded nano-scale metal Pt nanoparticles is 1-2 nm, and the Pt metal loading in the molecular sieve-loaded nano-scale metal Pt nanoparticles is 1wt%; The metal nano-mesoporous structure catalyst contains Ga, Na, Si, and Al; the adsorption critical diameter of the metal nano-mesoporous structure catalyst is no more than 4 nm; The hydrogen input pipeline (301) is connected to the gas phase medium input port of the reactor (101) through the valve 1 (201), and the hydrogen output pipeline (302) is connected to the gas phase medium output port of the reactor (101) through the valve 2 (202); the hydrogen before purification is input from the hydrogen input pipeline (301), and the content of gas phase sulfur in the hydrogen before purification is ≤0.02 µmol / mol; the hydrogen after purification is output from the hydrogen output pipeline (302), and the content of gas phase sulfur in the hydrogen after purification is ≤0.004 µmol / mol.

2. A hydrogen purification device for desulfurization using a metal nano-mesoporous structure catalyst according to claim 1, characterized in that: The sieve plate assembly (104) is composed of a metal filter, a sieve plate and a support frame. The sieve plate is supported by the support frame at the bottom of the reactor (101). The metal filter is installed on the sieve plate. The material of the metal filter is stainless steel 316L, and the mesh number of the filter is 18 to 30.

3. The hydrogen purification device for desulfurization using a metal nano-mesoporous structure catalyst according to claim 1, characterized in that: The gas pressure of the valve 1 (201) is controlled by the pressure regulator PIC.

4. The hydrogen purification device for desulfurization using a metal nano-mesoporous structure catalyst according to claim 1, characterized in that: A catalyst discharge port (105) is provided on the side of the reactor (101) corresponding to the packing layer (103).

5. The hydrogen purification device for desulfurization using a metal nano-mesoporous structure catalyst according to claim 1, characterized in that: The reactor (101) is provided with a temperature sensor PT for detecting the temperature of the upper portion of the packing layer (103) and a temperature sensor TT for detecting the temperature of the lower portion of the packing layer (103).

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