Hydrogen purification system based on cooperation of adsorption and membrane separation

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By using a multi-stage adsorption bed and a two-stage membrane separation structure, combined with activated carbon, activated alumina and MOF materials, the problems of high energy consumption and low purity in existing hydrogen purification methods have been solved, and efficient hydrogen purification and high-purity separation of refinery dry gas have been achieved.

CN223969736UActive Publication Date: 2026-03-06SHAANXI HYDROGEN ENERGY RES INST CO LTD

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Patent Information

Authority / Receiving Office: CN · China
Patent Type: Utility models(China)
Current Assignee / Owner
Filing Date: 2025-04-02
Publication Date: 2026-03-06

AI Technical Summary

Technical Problem

Existing hydrogen purification methods suffer from high energy consumption, low purity, and high cost, making it difficult to effectively utilize hydrogen resources in refinery dry gas.

Method used

Employing a multi-stage adsorption bed and a two-stage membrane separation structure, and combining adsorbents such as activated carbon, activated alumina, molecular sieves, and MOF materials, this system achieves efficient hydrogen purification of refinery dry gas through inlet gas pretreatment, multi-stage adsorption, and two-stage membrane separation.

Benefits of technology

It achieves low-energy consumption and high-purity hydrogen separation from refinery dry gas, reduces impurity retention, and improves hydrogen purity and utilization efficiency.

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Abstract

The utility model relates to the technical field of hydrogen purification, and discloses a hydrogen purification system based on cooperation of adsorption and membrane separation. The system comprises a gas inlet pretreatment unit and a composite adsorption unit, an inlet of the gas inlet pretreatment unit is externally connected with refinery dry gas, and an outlet of the gas inlet pretreatment unit is communicated with an inlet of the composite adsorption unit; the hydrogen purification system based on adsorption and membrane separation cooperation further comprises a membrane separation unit and a hydrogen storage unit, an inlet of the membrane separation unit is communicated with an outlet of the composite adsorption unit, and an inlet of the hydrogen storage unit is communicated with an outlet of the membrane separation unit. The membrane separation unit comprises a two-stage membrane separation membrane assembly and a pressure difference regulation and control device. The hydrogen purification system based on cooperation of adsorption and membrane separation can realize separation and purification of hydrogen from refinery dry gas with low energy consumption and high purity.

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Description

Technical Field

[0001] This invention belongs to the field of hydrogen purification technology, specifically relating to a hydrogen purification system based on the synergistic effect of adsorption and membrane separation. Background Technology

[0002] In the petroleum refining industry, refinery dry gas refers to the semi-finished gas produced during the processing of oil in refineries. Refinery dry gas mainly originates from secondary processing of crude oil, such as catalytic cracking, delayed coking, and continuous reforming units, and is rich in hydrogen, C1, C2, C3, and other light hydrocarbon resources. In traditional refineries, dry gas is often used as supplementary fuel gas, failing to efficiently utilize its hydrogen content. This not only wastes resources but also puts pressure on the environment.

[0003] Currently, hydrogen purification methods include cryogenic purification, pressure swing adsorption (PSA), shallow-cooled oil absorption, and membrane separation. Cryogenic purification requires large-scale equipment and high energy consumption, and it is difficult to achieve high purity. While membrane separation is convenient to operate, it is easily deactivated by organic matter and requires additional pretreatment. Existing single purification methods have certain limitations in terms of cost, efficiency, and purity, making it difficult to meet the demand for high-purity hydrogen. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides a hydrogen purification system based on the synergistic combination of adsorption and membrane separation. Through a multi-stage adsorption bed and a two-stage membrane separation structure, it achieves the goal of low energy consumption and high purity in the separation and purification of hydrogen from refinery dry gas.

[0005] To achieve the goal of low energy consumption and high purity in the separation and purification of hydrogen from dry gas in refineries, this utility model provides the following technical solution:

[0006] A hydrogen purification system based on the synergistic combination of adsorption and membrane separation is disclosed. The system includes: an inlet pretreatment unit and a composite adsorption unit. The inlet of the inlet pretreatment unit is connected to refinery dry gas, and the outlet of the inlet pretreatment unit is connected to the inlet of the composite adsorption unit. The hydrogen purification system based on the synergistic combination of adsorption and membrane separation further includes: a membrane separation unit and a hydrogen storage unit. The inlet of the membrane separation unit is connected to the outlet of the composite adsorption unit, and the inlet of the hydrogen storage unit is connected to the outlet of the membrane separation unit.

[0007] Furthermore, the intake pretreatment unit includes: a filter device and a drying device connected to the outlet of the filter device, the filter device being connected to refinery dry gas, and the outlet of the drying device being connected to the inlet of the composite adsorption unit.

[0008] Furthermore, the composite adsorption unit includes: a multi-stage adsorption bed, the outlet of the air inlet pretreatment unit is connected to the inlet of the multi-stage adsorption bed, and the outlet of the multi-stage adsorption bed is connected to the inlet of the membrane separation unit;

[0009] Preferably, the multi-stage adsorption bed is two-stage, including: a first-stage adsorption bed and a second-stage adsorption bed, wherein the inlet of the first-stage adsorption bed is connected to the outlet of the air intake pretreatment unit, the outlet of the first-stage adsorption bed is connected to the inlet of the second-stage adsorption bed, and the inlet of the membrane separation unit is connected to the outlet of the second-stage adsorption bed.

[0010] Furthermore, the membrane separation unit includes: a multi-stage membrane separation membrane module and a pressure difference control device. The inlet of the multi-stage membrane separation membrane module is connected to the outlet of the composite adsorption unit through a pipeline, and the outlet of the multi-stage membrane separation membrane module is connected to the inlet of the hydrogen storage unit.

[0011] Preferably, the multi-stage membrane separation module is two-stage, including: a first-stage membrane separation module and a second-stage membrane separation module. The inlet of the first-stage membrane separation module is connected to the outlet of the composite adsorption unit through a pipe. The outlet of the first-stage membrane separation module is connected to the inlet of the second-stage membrane separation module. The outlet of the second-stage membrane separation module is connected to the inlet of the hydrogen storage unit.

[0012] Furthermore, the membrane separation unit also includes a temperature control device, which includes a refrigeration device.

[0013] Furthermore, the hydrogen storage unit includes a hydrogen storage device, which includes a frame and a gas cylinder group. The gas cylinder group is installed in a rectangular array in the inner cavity of the frame, and the total inlet of the gas cylinder group is connected to the outlet of the second-stage membrane separation component.

[0014] Compared with existing technologies, this invention provides a hydrogen purification system based on the synergistic effect of adsorption and membrane separation, which has the following advantages:

[0015] First, multi-stage adsorption beds can effectively remove impurity gases and have advantages such as low energy consumption and no secondary pollution.

[0016] Secondly, a two-stage membrane separation structure is adopted. In the first-stage membrane module, under a certain pressure difference, most of the hydrogen gas preferentially permeates through the membrane pores, while some larger impurities, due to their larger molecular size, cannot pass through the membrane pores and are thus retained. After the first-stage membrane separation, the purity of the gas is improved to a certain extent, while reducing the processing load of subsequent membrane modules.

[0017] Second-stage membrane separation: The gas after the first-stage membrane separation then enters the second-stage membrane module. The pore size and chemical properties of the second-stage membrane module are further optimized, enabling more precise separation of specific components from the remaining impurities. For some smaller impurity molecules that remain after the first-stage membrane separation but have properties similar to hydrogen, the second-stage membrane module, through its finer pore structure and chemoselectivity, can further retain these impurities, thereby further improving the purity of the hydrogen. This two-stage membrane structure achieves highly efficient purification of hydrogen gas through the synergistic effect of different membrane modules. Attached Figure Description

[0018] Figure 1 This is a diagram showing the unit composition of a hydrogen purification system based on the synergistic combination of adsorption and membrane separation.

[0019] Figure 2 This is a structural diagram of a hydrogen purification system based on the synergistic combination of adsorption and membrane separation.

[0020] In the diagram: 1. Filtration device; 2. Drying device; 3. First-stage adsorption bed; 4. Second-stage adsorption bed; 5. First-stage membrane separation module; 6. Second-stage membrane separation module; 7. Hydrogen storage device. Detailed Implementation

[0021] The technical solutions of the present utility model will be clearly and completely described below with reference to the accompanying drawings of the embodiments. Obviously, the described embodiments are only some embodiments of the present utility model, and not all embodiments. Based on the embodiments of the present utility model, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the protection scope of the present utility model.

[0022] A hydrogen purification system based on the synergy of adsorption and membrane separation, the system comprising: an inlet pretreatment unit and a composite adsorption unit, wherein the inlet of the inlet pretreatment unit is connected to refinery dry gas, and the outlet of the inlet pretreatment unit is connected to the inlet of the composite adsorption unit;

[0023] The hydrogen purification system based on the synergy of adsorption and membrane separation further includes: a membrane separation unit and a hydrogen storage unit, wherein the inlet of the membrane separation unit is connected to the outlet of the composite adsorption unit, and the inlet of the hydrogen storage unit is connected to the outlet of the membrane separation unit.

[0024] Furthermore, the intake pretreatment unit includes: a filter device 1 and a drying device 2 connected to the outlet of the filter device. The filter device is connected to dry gas from the refinery and is used to perform preliminary filtration of the hydrogen-containing gas entering the system to remove solid impurities. The outlet of the drying device 2 is connected to the inlet of the composite adsorption unit and is used to dry the dry gas from the refinery to remove moisture, ensuring that the subsequent processing can proceed normally.

[0025] In a preferred embodiment, the composite adsorption unit includes a multi-stage adsorption bed, the outlet of the air pretreatment unit is connected to the inlet of the multi-stage adsorption bed, and the outlet of the multi-stage adsorption bed is connected to the inlet of the membrane separation unit.

[0026] Hydrogen-containing gas passes through a multi-stage adsorption bed, where it sequentially adsorbs C. n H m (n≥2, m is an integer) and other impurity components. The adsorption conditions (such as temperature, pressure, flow rate, etc.) of each adsorption bed can be optimized and adjusted according to the different types of impurities.

[0027] The multi-stage adsorption bed is equipped with a composite adsorbent, which includes one or more of the following: activated carbon, activated alumina, molecular sieve, and MOF (metal-organic framework) materials.

[0028] Furthermore, the multi-stage adsorption bed is two-stage, including: a first-stage adsorption bed 3 and a second-stage adsorption bed 4. The inlet of the first-stage adsorption bed 3 is connected to the outlet of the air intake pretreatment unit, the outlet of the first-stage adsorption bed 3 is connected to the inlet of the second-stage adsorption bed 4, and the inlet of the membrane separation unit is connected to the outlet of the second-stage adsorption bed 4.

[0029] In a preferred embodiment, the membrane separation unit includes: a multi-stage membrane separation module and a pressure differential control device. The inlet of the multi-stage membrane separation module is connected to the outlet of the composite adsorption unit via a pipeline, and the outlet of the multi-stage membrane separation module is connected to the inlet of the hydrogen storage unit.

[0030] Ensure that gas can stably enter the membrane separation unit from the adsorption unit. The membrane separation modules are connected by appropriate pipes and valves so that the gas can be sequentially passed through different stages of membrane modules for separation.

[0031] The multi-stage membrane separation module is two-stage, including a first-stage membrane separation module 5 and a second-stage membrane separation module 6. The inlet of the first-stage membrane separation module 5 is connected to the outlet of the composite adsorption unit through a pipe. The outlet of the first-stage membrane separation module 5 is connected to the inlet of the second-stage membrane separation module 6. The outlet of the second-stage membrane separation module 6 is connected to the inlet of the hydrogen storage unit.

[0032] The pressure difference control device is used to adjust the pressure difference based on the membrane characteristics and gas composition. The pressure difference between the inlet and the outlet of the first-stage membrane separation component 5 is set to 1-2 MPa, and the pressure difference between the outlet of the first-stage membrane separation component 5 and the outlet of the second-stage membrane separation component 6 is also controlled at 1-2 MPa. By reasonably controlling the pressure difference, impurities can be retained to the maximum extent while ensuring a high hydrogen permeability, thereby improving the purity of the hydrogen.

[0033] Each stage of the membrane module has different pore sizes and chemical functions to achieve the stepwise separation of impurities of varying densities. Gas first enters the first-stage membrane separation module 5. Under a certain pressure difference, most hydrogen gas preferentially permeates through the membrane pores, while some larger impurities, due to their larger molecular size, cannot pass through the membrane pores and are thus retained. After passing through the first-stage membrane separation module 5, the purity of the gas is improved to a certain extent.

[0034] The gas passing through the first-stage membrane separation module 5 then enters the second-stage membrane separation module 6. The membrane pore size and chemical function of the second-stage membrane separation module 6 are further optimized, enabling more precise separation of specific components from the remaining impurities, thus further improving the purity of hydrogen. This two-stage membrane separation structure achieves highly efficient purification of hydrogen gas through the synergistic effect of different membrane modules, significantly improving the purity of hydrogen.

[0035] The membrane separation unit further includes a temperature control device for controlling the temperature within the membrane separation unit; further, the temperature control device includes a refrigeration device.

[0036] The hydrogen storage unit includes a hydrogen storage device 7, which includes a frame and a gas cylinder group. The gas cylinder group is installed in a rectangular array in the inner cavity of the frame, and the total inlet of the gas cylinder group is connected to the outlet of the second-stage membrane separation component 6.

[0037] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitations, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0038] Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the present invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A hydrogen purification system based on the synergy of adsorption and membrane separation, characterized in that: The system comprises: a gas inlet pretreatment unit and a composite adsorption unit, the gas inlet pretreatment unit is externally connected with a refinery dry gas at the inlet, and the outlet of the gas inlet pretreatment unit is in communication with the inlet of the composite adsorption unit. The hydrogen purification system based on the cooperation of adsorption and membrane separation further comprises: a membrane separation unit and a hydrogen storage unit, the inlet of the membrane separation unit is in communication with the outlet of the composite adsorption unit, and the inlet of the hydrogen storage unit is in communication with the outlet of the membrane separation unit.

2. The hydrogen purification system based on the synergy of adsorption and membrane separation according to claim 1, characterized in that: The gas inlet pretreatment unit comprises: a filtering device (1) and a drying device (2) in communication with the outlet of the filtering device, the inlet of the filtering device (1) is externally connected with a refinery dry gas, and the outlet of the drying device (2) is in communication with the inlet of the composite adsorption unit.

3. The hydrogen purification system based on the synergy of adsorption and membrane separation according to claim 1, characterized in that: The composite adsorption unit comprises: a multi-stage adsorption bed, the outlet of the gas inlet pretreatment unit is in communication with the inlet of the multi-stage adsorption bed, and the outlet of the multi-stage adsorption bed is in communication with the inlet of the membrane separation unit.

4. The hydrogen purification system based on the synergy of adsorption and membrane separation according to claim 3, characterized in that: The multi-stage adsorption bed is two-stage, comprising: a first-stage adsorption bed (3) and a second-stage adsorption bed (4), the inlet of the first-stage adsorption bed (3) is in communication with the outlet of the gas inlet pretreatment unit, the outlet of the first-stage adsorption bed (3) is in communication with the inlet of the second-stage adsorption bed (4), and the inlet of the membrane separation unit is in communication with the outlet of the second-stage adsorption bed (4).

5. The hydrogen purification system based on the synergy of adsorption and membrane separation according to claim 1, characterized in that: The membrane separation unit comprises: a multi-stage membrane separation membrane assembly and a pressure difference regulating device, the inlet of the multi-stage membrane separation membrane assembly is in communication with the outlet of the composite adsorption unit through a pipeline, and the outlet of the multi-stage membrane separation membrane assembly is in communication with the inlet of the hydrogen storage unit.

6. The hydrogen purification system based on the synergy of adsorption and membrane separation according to claim 5, characterized in that: The multi-stage membrane separation membrane assembly is two-stage, comprising: a first-stage membrane separation assembly (5) and a second-stage membrane separation assembly (6), the inlet of the first-stage membrane separation assembly (5) is in communication with the outlet of the composite adsorption unit through a pipeline, the outlet of the first-stage membrane separation assembly (5) is in communication with the inlet of the second-stage membrane separation assembly (6), and the outlet of the second-stage membrane separation assembly (6) is in communication with the inlet of the hydrogen storage unit.

7. The hydrogen purification system based on the synergy of adsorption and membrane separation according to claim 1, characterized in that: The membrane separation unit further comprises: a temperature regulating device.

8. The hydrogen purification system based on the synergy of adsorption and membrane separation according to claim 7, characterized in that: The temperature regulating device comprises: a refrigeration device.

9. The hydrogen purification system based on the synergy of adsorption and membrane separation according to claim 6, characterized in that: The hydrogen storage unit comprises: a hydrogen storage device (7), the hydrogen storage device (7) comprises: a frame and a group of gas cylinders, the group of gas cylinders is installed in a rectangular array in the inner cavity of the frame, and the total inlet of the group of gas cylinders is in communication with the outlet of the second-stage membrane separation assembly (6).