CN115228235A - Hydrogen-helium gas separation device - Google Patents
Hydrogen-helium gas separation device Download PDFInfo
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- CN115228235A CN115228235A CN202210514933.7A CN202210514933A CN115228235A CN 115228235 A CN115228235 A CN 115228235A CN 202210514933 A CN202210514933 A CN 202210514933A CN 115228235 A CN115228235 A CN 115228235A
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/0407—Constructional details of adsorbing systems
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/42—Auxiliary equipment or operation thereof
- B01D46/44—Auxiliary equipment or operation thereof controlling filtration
- B01D46/46—Auxiliary equipment or operation thereof controlling filtration automatic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/56—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with multiple filtering elements, characterised by their mutual disposition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/56—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with multiple filtering elements, characterised by their mutual disposition
- B01D46/62—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with multiple filtering elements, characterised by their mutual disposition connected in series
- B01D46/64—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with multiple filtering elements, characterised by their mutual disposition connected in series arranged concentrically or coaxially
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/0454—Controlling adsorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B23/00—Noble gases; Compounds thereof
- C01B23/001—Purification or separation processes of noble gases
- C01B23/0036—Physical processing only
- C01B23/0052—Physical processing only by adsorption in solids
- C01B23/0057—Physical processing only by adsorption in solids characterised by the adsorbent
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
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- Chemical & Material Sciences (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a hydrogen-helium gas separation device which comprises a hydrogen storage alloy system, a heat exchange structure and a control system, wherein hydrogen is adsorbed by the hydrogen storage alloy system, so that the separation of the hydrogen and the helium is realized. By adopting the device, the adsorption effect of the hydrogen storage alloy on hydrogen is utilized, and the plurality of groups of bed bodies are connected in parallel, so that the continuous separation and recovery of the hydrogen-helium mixture gas with different concentrations can be realized.
Description
Technical Field
The invention relates to the technical field of gas separation and purification, in particular to a separation device for hydrogen-helium mixed gas.
Background
Helium is one of indispensable rare strategic materials for national defense military industry and high-tech industry development, and is widely applied to the fields of military industry, scientific research, petrifaction, refrigeration, medical treatment, semiconductors, superconducting experiments, deep sea diving, production of optoelectronic products and the like. China belongs to a poor helium country, and the total amount of natural gas and helium gas resources is less and the content is low. At present, the self-sufficient rate of helium in China is low, and helium supply depends on import for a long time. The helium is extracted from the natural gas, so that the helium supply for the petroleum in China is guaranteed, the energy field is expanded, and the strategic significance for guaranteeing the national energy safety is achieved.
At present, the process for extracting helium from natural gas at home and abroad mainly comprises a cryogenic method and a membrane separation method.
Cryogenic rectification is a commonly used method in most large and medium natural gas recovery helium plants. The principle is that liquid nitrogen is used as a refrigerant (about-190 ℃), hydrocarbons and other components in the natural gas are gradually condensed, and helium is separated from other components in the natural gas due to the extremely low boiling point of the helium. For example, chinese patent (ZL 201210255340. X) discloses a method for extracting helium from natural gas, comprising the steps of: A. feeding raw material natural gas containing helium into a main heat exchanger for cooling; B. b, feeding the mixture obtained by cooling in the step A into a separation tower, heating the mixture, cooling at least part of steam by a condensing evaporator at the tower top to obtain primary crude helium, and purifying the primary crude helium to obtain a crude helium product; C. b, decompressing and throttling part of liquid at the bottom of the separation tower, then entering a tower top condensation evaporator through a pipeline to serve as a cold source of the condensation evaporator, and exchanging heat with the steam in the step B; D. and (4) determining whether the LNG product obtained by the cold source in the step C after the heat exchange with the steam in the step B needs to be obtained from the evaporation detection of the condensation evaporator according to the cold balance requirement. Chinese patent (ZL 201210513423.4) discloses a natural gas low-temperature helium extraction system and method, wherein a post-expansion and nitrogen circulation refrigeration two-tower separation technology is adopted, cold energy of a device is fully recovered to pre-cool raw material natural gas, the system can be suitable for natural gas with extremely low helium content, and meanwhile, the system has the characteristics of low energy consumption, high hydrogen recovery rate, investment saving, flexible operation, strong variable working condition adaptability and the like. Although the method can realize the separation of helium, the method also has certain problems, which are mainly reflected in that 1) along with the continuous reduction of the refrigeration temperature, the energy consumption of unit refrigeration capacity is increased sharply, so that higher and more rigorous requirements are provided for how to efficiently refrigerate, how to reasonably and efficiently utilize refrigeration capacity, and design, manufacture and operation of equipment. 2) Natural gas is a multi-component mixture, and low-temperature phase equilibrium is the basis of cryogenic helium extraction of natural gas. Due to the limitations of the freezing point and solubility of the substances, more substances can cause low-temperature blockage with the decrease of the refrigeration temperature, and the operation of the equipment is unstable. 3) The equipment mostly adopts metals such as stainless steel, aluminum, copper and the like, requires good low-temperature resistance, relates to the problems of transition connection of different materials, multilayer vacuum shielding heat insulation and the like, and puts more demands on high-vacuum equipment, helium leak detection, materials, processes and the like.
In addition to cryogenic separation, gas separation membranes are a relatively new separation technology. The gas components are subjected to mass transfer on a high molecular polymer film (cellulose acetate, polypropylene, polysulfone, polyimide and the like) based on the principle of dissolution and diffusion, and the effect of separating the components is achieved according to different solubilities and diffusion rates of different gas components in the film material. When a mixture of two or more gases is passed through a polymer membrane, the permeation rates of the helium and hydrogen components are much higher than those of nitrogen and methane and other hydrocarbons. Membrane separation is combined with other processes to obtain a permeate gas having hydrogen helium as the main component. For example, in the literature (initial application of membrane separation and pressure swing adsorption combined process in natural gas stripping, scientific and technical innovation, 2021.15), it is mentioned that by arranging a two-end membrane separation system, optimizing a membrane unit configuration scheme, and reasonably designing a cycle of gas analysis of a PSA unit, a helium recovery rate of >87% of the whole can be maintained while a high-purity helium product with He + H2 of 99.99% or more is prepared. How to separate the hydrogen from the helium becomes a key to whether the process is feasible.
For hydrogen-helium separation, there are methods such as palladium metal membrane, catalytic oxidation, metal hydride and the like. The palladium metal membrane is limited by the cost of noble metal palladium, is mainly applied to small-scale gas separation occasions such as separation of hydrogen isotopes and the like at present, and cannot be directly applied to large-scale gas separation occasions. The catalytic oxidation is to oxidize hydrogen into water or methane under the action of a catalyst. For example, chinese patent (CN 201810308806.5) discloses a process for purifying helium from hydrogen-containing helium exhaust, which comprises supplementing hydrogen with carbon monoxide or carbon dioxide or a mixture of the two, and catalytically converting the hydrogen into methane; or supplementing excessive oxygen to catalytically convert hydrogen into water. Catalytic oxidation cannot tolerate high levels of hydrogen and is less effective if the feed gas source composition fluctuates. The metal hydride can effectively remove the hydrogen in the hydrogen-helium mixed gas by utilizing the reaction of the hydrogen storage alloy and the hydrogen. For example, the invention discloses a normal-temperature hydrogen-helium separation and storage integrated device and a method thereof in chinese patent (CN 202110278127. X), wherein the normal-temperature hydrogen-helium separation and storage integrated device comprises a booster pump, a flowmeter, a first hydrogen storage bed, a second hydrogen storage bed, a quadrupole mass spectrum, a booster pump, a helium storage tank and a hydrogen storage tank which are connected in sequence. Introducing the hydrogen-helium mixed gas into the first hydrogen storage bed, and simultaneously controlling the flow of the hydrogen-helium mixed gas, wherein the first hydrogen storage bed is in a working state and the second hydrogen storage bed is in an idle state; when the quadrupole mass spectrum has a hydrogen signal, switching and introducing hydrogen-helium mixed gas into a second hydrogen storage bed; and recovering all the valves to a closed state until no gas is input at the front end of the booster pump, and finishing the separation of the mixed gas. The invention realizes the integration of continuous and complete separation of high-purity hydrogen and high-purity helium at normal temperature and separation and storage of hydrogen, but because the internal filling structure is not considered, the bed body is blocked or stacked due to powder expansion in the working process of the hydrogen storage bed, gas open circuit or short circuit is caused, and the bed body is invalid.
Although the above technologies and process routes can realize separation of helium, the process is complicated, or the energy consumption is high, or the performance and the service life are poor, and the practical use requirement of hydrogen-helium gas separation is difficult to meet.
Disclosure of Invention
The invention aims to provide a brand-new hydrogen-helium gas separation device, which realizes the separation of hydrogen and helium by utilizing the adsorption effect of hydrogen storage alloy on hydrogen. After adsorption saturation, the regeneration of the hydrogen storage alloy bed can be realized by heating the hydrogen storage alloy bed body. The separation device has the characteristics of high gas separation degree, simplicity in operation and low operation cost.
In order to solve the technical problem, the invention provides a hydrogen-helium gas separation device which comprises a hydrogen storage alloy system, a heat exchange structure and a control system, wherein hydrogen is adsorbed by the hydrogen storage alloy system, so that the separation of the hydrogen and the helium is realized.
The hydrogen storage alloy system comprises a bed body, hydrogen storage alloy, a filter and a valve, wherein the hydrogen storage alloy is filled in the bed body, and an air inlet and an air outlet are reserved at two ends of the bed body and are controlled to be opened and closed through the valve.
Wherein the hydrogen storage alloy system comprises at least three groups of beds.
Wherein, the hydrogen storage alloy and the heat conduction material are mixed and filled, layered and filled, and are placed in the bed body.
Wherein, the heat conduction material comprises products such as wire mesh, foil and the like made of materials such as aluminum, copper, stainless steel and the like.
Wherein, the layered filling adopts a filter plate, a porous material, a honeycomb material and the like as materials of the separation layers, and hydrogen storage alloys are filled in each separation layer.
Wherein, the hydrogen storage alloy is AB5, AB2, AB series hydrogen storage alloy, including alloy composed of two or more of lanthanum, nickel, titanium, zirconium, cerium, cobalt, iron, aluminum, manganese, vanadium, yttrium, niobium, molybdenum.
Wherein the hydrogen storage alloy is coated by physical vapor deposition or chemical method, and the coating material is Pd, ni, cu, co, ag, au, pt, al 2 O 3 、SiO 2 One or more of the above components are compounded.
The heat exchange structure can be one or more of a jacketed heat exchanger, a double-pipe heat exchanger, a coiled heat exchanger, a finned heat exchanger and a plate heat exchanger.
The control system comprises a touch screen and a PLC control system.
The PLC control system is communicated with temperature, pressure and flow sensors in the device, monitors the running state in real time, controls the opening and closing of the valves and realizes the automatic running of at least three groups of hydrogen storage beds.
The invention has the advantages of
The hydrogen-helium gas separation device provided by the invention realizes the separation of hydrogen and helium by utilizing the adsorption effect of the hydrogen storage alloy on hydrogen. After adsorption saturation, the regeneration of the hydrogen storage alloy bed can be realized by heating the hydrogen storage alloy bed body. The hydrogen storage alloy powder is coated, so that the volume expansion of the hydrogen storage alloy powder is effectively inhibited on the premise of not influencing the hydrogen absorption of the hydrogen storage alloy, and the service life of the alloy powder is prolonged. The mixed material is mixed with a heat conduction material and filled in layers, so that the heat exchange efficiency of the bed body can be obviously improved, the hydrogen absorption and desorption rate of the hydrogen storage alloy material can be improved, the agglomeration and segregation phenomena caused by the impact of high-speed airflow on the alloy powder and the gas short circuit caused by the agglomeration and segregation phenomena can be inhibited, and the stability of the bed body can be improved. The device has the characteristics of high gas separation degree, simple operation and low operation cost. The hydrogen-helium gas separation device adopts advanced automatic control technology, is matched with a plurality of sensor acquisition operation devices, can realize automatic operation/regeneration of the device, and has the characteristics of high automation degree and reliable operation.
Drawings
FIG. 1 is a schematic structural diagram of a hydrogen-helium gas separation apparatus provided by the present invention;
FIG. 2 is a schematic diagram of the bed structure of the hydrogen-helium gas separation device provided by the present invention.
Detailed Description
A hydrogen-helium gas separation device comprises a hydrogen storage alloy system, a heat exchange structure and a control system, wherein hydrogen is adsorbed by the hydrogen storage alloy system, so that the separation of the hydrogen and the helium is realized.
The hydrogen storage alloy system comprises a bed body, hydrogen storage alloy, a filter and a valve, wherein the hydrogen storage alloy is filled in the bed body, and an air inlet and an air outlet are reserved at two ends of the bed body and are controlled to be switched on and off through the valve.
The hydrogen storage alloy system comprises at least three groups of bed bodies, and can ensure that at least one group of bed bodies works (absorbs hydrogen), at least one group of bed bodies is adsorbed and saturated for regeneration, and at least one group of bed bodies is regenerated for standby, thereby realizing the continuous work of the whole set of device.
In order to ensure the service life of the hydrogen storage alloy, one of the modes of mixing and filling with heat conducting materials, layered filling and the like is adopted. The heat conducting material comprises products such as wire mesh and foil made of materials such as aluminum, copper and stainless steel. The layered filling adopts a filter plate, a porous material, a honeycomb material and the like as materials of the partition layers, and hydrogen storage alloys are filled in each partition layer.
Wherein, the hydrogen storage alloy is AB5, AB2, AB series hydrogen storage alloy, including alloy composed of two or more of lanthanum, nickel, titanium, zirconium, cerium, cobalt, iron, aluminum, manganese, vanadium, yttrium, niobium, molybdenum.
Coating the surface of the hydrogen storage alloy by physical vapor deposition or chemical method, wherein the coating material is Pd, ni, cu, co, ag, au, pt or Al 2 O 3 、SiO 2 One or more of the above components are compounded. Hydrogen can permeate the coating material and be absorbed by the hydrogen storage material; meanwhile, the coating material can inhibit the expansion of the hydrogen storage material, prevent the further pulverization of the hydrogen storage material and effectively prolong the cycle life of the hydrogen storage material.
The heat exchange structure can adopt one or more of a jacketed heat exchanger, a double-pipe heat exchanger, a coiled heat exchanger, a finned heat exchanger and a plate heat exchanger to realize heating and cooling of the hydrogen storage material and ensure smooth hydrogen absorption and desorption.
The control system comprises a touch screen and a PLC control system, and the automatic operation of the hydrogen-helium separation device is realized in a mode of the PLC control system and the touch screen. The PLC control system is communicated with temperature, pressure and flow sensors in the device, monitors the running state in real time, controls the opening and closing of the valves and realizes the automatic running of at least three groups of hydrogen storage beds. The PLC control system also controls heating and refrigerating equipment, and the heating/cooling state is switched along with the working state of the hydrogen storage alloy bed body.
Different alloy components are selected to form a two-stage or three-stage separation device, the alloy with a higher hydrogen absorption platform is selected at the front stage, and the alloy with a lower hydrogen absorption platform is sequentially selected at the subsequent stage. In the hydrogen-helium gas separation device, after the hydrogen-helium mixture is subjected to primary separation, the concentration of helium in hydrogen in the hydrogen storage tank is less than 1ppm, and the concentration of hydrogen in helium in the helium storage tank is less than 1000ppm; the helium gas after the first-stage separation can be subjected to secondary separation, and the concentration of hydrogen in the helium gas storage tank is less than 1ppm after the second-stage separation.
Embodiments of the present invention will be described in detail below with reference to examples and drawings, by which how to apply technical means to solve technical problems and achieve a technical effect can be fully understood and implemented.
As shown in fig. 1 and 2, the present invention provides a hydrogen-helium gas separation apparatus, which includes a hydrogen storage alloy system, a heat exchange structure and a control system, wherein the hydrogen storage alloy system adsorbs hydrogen gas to realize separation of hydrogen gas and helium gas. As shown in figure 2, the hydrogen storage alloy system comprises three bed bodies A, B and C, as shown in figure 1, the hydrogen storage alloy is filled in the bed bodies, air inlets 1-1 and air outlets 1-6 are reserved at two ends of the bed bodies, and the on-off is controlled by valves. The outer side of the bed body is also provided with a jacket 1-2, the bed body is internally provided with a plurality of partition plates 1-3 for isolating the hydrogen storage alloy, in order to ensure the service life of the hydrogen storage alloy, a mode of mixing and filling the hydrogen storage alloy with heat conduction materials 1-4 is adopted, and heat exchange media 1-5 are introduced into a gap between the jacket and the outer wall of the bed body.
Example 1
The hydrogen-helium mixed gas is directly introduced into a hydrogen-helium gas separation device, the mixed gas firstly enters a low-temperature adsorption separation bed area, hydrogen in the mixed gas is adsorbed by a separation material after passing through a low-temperature adsorption bed, and the mixed gas after dehydrogenation, namely helium, flows out through a pipeline and enters a helium storage tank. After the hydrogen adsorption amount of the hydrogen storage material in the low-temperature adsorption bed region reaches saturation, the heat exchange system is started, the temperature of the low-temperature bed region is raised, so that the adsorbed hydrogen is released, and the hydrogen flows out of the low-temperature bed region through a pipeline and enters a hydrogen storage tank. The hydrogen storage alloy system consists of three groups of bed bodies, and can ensure that at least one group of bed bodies works (absorbs hydrogen), at least one group of bed bodies absorbs saturated regeneration, and at least one group of bed bodies finishes regeneration for standby, thereby realizing the continuous work of the whole set of device.
In this embodiment, the raw material gas is a hydrogen-helium mixture containing 50% helium and 50% hydrogen, ni-coated LaNiAlMn is selected as a separation material in the bed body, an aluminum foil is selected as a heat conduction material, the separation material and the heat conduction material are mixed and filled, and the weight ratio of the hydrogen storage alloy to the aluminum foil is 5:1, the filter plate is used as a separating layer material, and a sleeve type heat exchanger is adopted as a heat exchange structure. The hydrogen in helium in the helium tank and the helium in hydrogen in the hydrogen tank were measured using a gas chromatograph. The results are shown in Table 1.
Table 1 shows the results of the chromatographic measurements in example 1
Example 2
The hydrogen-helium mixed gas is directly introduced into a hydrogen-helium gas separation device, the mixed gas firstly enters a low-temperature adsorption separation bed area, hydrogen in the mixed gas is adsorbed by a separation material after passing through a low-temperature adsorption bed, and the mixed gas after hydrogen removal, namely helium, flows out through a pipeline and enters a helium storage tank. After the hydrogen adsorption amount of the hydrogen storage material in the low-temperature adsorption bed area reaches saturation, the heat exchange system is started, the temperature of the low-temperature bed area is raised, so that the adsorbed hydrogen is released and flows out of the low-temperature bed area through a pipeline and then enters a hydrogen storage tank. The hydrogen storage alloy system consists of three groups of bed bodies, and can ensure that at least one group of bed bodies works (absorbs hydrogen), at least one group of bed bodies absorbs saturated regeneration, and at least one group of bed bodies finishes regeneration for standby, thereby realizing the continuous work of the whole set of device.
In this embodiment, the raw material gas is a hydrogen-helium mixture containing 60% helium and 40% hydrogen, cu-coated LaNiAl is selected as a separation material in the bed body, a stainless steel wire mesh is selected as a heat conduction material, the separation material and the heat conduction material are mixed and filled, and the weight ratio of the hydrogen storage alloy to the stainless steel wire mesh is 4:1, the filter plate is used as a separating layer material, and a sleeve type heat exchanger is adopted as a heat exchange structure. The hydrogen in helium in the helium tank and the helium in hydrogen in the hydrogen tank were measured using a gas chromatograph. The results are shown in Table 2.
Table 2 shows the results of the chromatographic measurement in example 2
Example 3
The hydrogen-helium mixed gas is directly introduced into a hydrogen-helium gas separation device, the mixed gas firstly enters a low-temperature adsorption separation bed area, hydrogen in the mixed gas is adsorbed by a separation material after passing through a low-temperature adsorption bed, and the mixed gas after dehydrogenation, namely helium, flows out through a pipeline and enters a helium storage tank. After the hydrogen adsorption amount of the hydrogen storage material in the low-temperature adsorption bed region reaches saturation, the heat exchange system is started, the temperature of the low-temperature bed region is raised, so that the adsorbed hydrogen is released, and the hydrogen flows out of the low-temperature bed region through a pipeline and enters a hydrogen storage tank. The hydrogen storage alloy system consists of three groups of bed bodies, and can ensure that at least one group of bed bodies works (absorbs hydrogen), at least one group of bed bodies absorbs saturated regeneration, and at least one group of bed bodies finishes regeneration for standby, thereby realizing the continuous work of the whole set of device.
In this embodiment, the raw material gas is a hydrogen-helium mixture containing 40% helium and 60% hydrogen, the separation device is composed of two stages, the bed body of the first stage system is made of Al 2 O 3 Coated TiMn 2 Selecting a stainless steel wire mesh as a heat conducting material as a separation material, mixing and filling the separation material and the heat conducting material, wherein the weight ratio of the hydrogen storage alloy to the aluminum foil is 6:1, a filter plate is used as a separating layer material, and a jacketed heat exchanger is adopted as a heat exchange structure. SiO is selected in the bed body of the second-stage system 2 Coated ZrCo is used as separating material, copper net is used as heat conducting material, the separating material and the heat conducting material are mixed and filled, and hydrogen storage alloyThe weight ratio of the copper mesh to the copper mesh is 3:1, a filter plate is used as a separating layer material, and a jacketed heat exchanger is adopted as a heat exchange structure. The hydrogen in helium in the helium tank and the helium in hydrogen in the hydrogen tank were measured using a gas chromatograph. The results are shown in Table 3.
Table 3 shows the results of the chromatographic measurements in example 3
Example 4
The hydrogen-helium mixed gas is directly introduced into a hydrogen-helium gas separation device, the mixed gas firstly enters a low-temperature adsorption separation bed area, hydrogen in the mixed gas is adsorbed by a separation material after passing through a low-temperature adsorption bed, and the mixed gas after dehydrogenation, namely helium, flows out through a pipeline and enters a helium storage tank. After the hydrogen adsorption amount of the hydrogen storage material in the low-temperature adsorption bed region reaches saturation, the heat exchange system is started, the temperature of the low-temperature bed region is raised, so that the adsorbed hydrogen is released, and the hydrogen flows out of the low-temperature bed region through a pipeline and enters a hydrogen storage tank.
The hydrogen storage alloy system consists of three groups of bed bodies, as shown in figure 2, mixed gas firstly enters a hydrogen-helium separation bed A from VA1 and is adsorbed by separation materials in the bed bodies, switches C1 and C4 in the heat exchange system are turned on at the moment, the rest of the mixed gas are turned off, the whole bed body is cooled, helium flows out through a switch VA2, and switches VB1, VC1, VA3, VB2, VB3, VC2 and VC3 are all in a closed state at the moment; when the separation material in the hydrogen-helium separation bed A reaches critical saturation, VB1 is opened, VA1 is closed, the mixed gas flows into the separation bed B, C2 and C5 are opened in the heat exchange system, the hydrogen in the mixed gas is adsorbed by the separation material in the separation bed B, and the separated helium flows into a helium storage tank from VB 2. Meanwhile, the separation bed A is heated, the switches H1 and H4 are opened, hydrogen in the separation material is heated and released, and the released hydrogen enters the hydrogen storage tank through the VA 3. Similarly, when the separation bed B is saturated in hydrogen absorption, the mixed gas enters the separation bed C, and the separation bed B heats and releases hydrogen, so that the circulation is carried out, and the continuous operation of the whole device is realized.
In this embodiment, the raw material gas is a hydrogen-helium mixture containing 40% helium and 60% hydrogen, and SiO is selected in the bed 2 Coated withLaNiAlMn is used as a separation material, a stainless steel wire net is used as a heat conduction material, the separation material and the heat conduction material are mixed and filled, and the weight ratio of the hydrogen storage alloy to the aluminum foil is 6:1, a filter plate is used as a separating layer material, and a jacketed heat exchanger is adopted as a heat exchange structure. The hydrogen in helium in the helium tank and the helium in hydrogen in the hydrogen tank were measured using a gas chromatograph. The results are shown in Table 4.
Table 4 shows the results of the chromatographic measurements in example 4
All of the above mentioned intellectual property rights are not intended to be restrictive to other forms of implementing the new and/or new products. Those skilled in the art will take advantage of this important information, and the foregoing will be modified to achieve similar performance. However, all modifications or alterations are based on the new products of the invention and belong to the reserved rights.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (10)
1. A hydrogen-helium gas separation device is characterized in that: the hydrogen storage alloy system adsorbs hydrogen to realize separation of hydrogen and helium.
2. The hydrogen-helium gas separation device according to claim 1, wherein: the hydrogen storage alloy system comprises a bed body, hydrogen storage alloy, a filter and a valve, wherein the hydrogen storage alloy is filled in the bed body, and an air inlet and an air outlet are reserved at two ends of the bed body and are controlled to be switched on and off through the valve.
3. The hydrogen-helium gas separation device according to claim 2, wherein: the hydrogen storage alloy system comprises at least three groups of beds.
4. The hydrogen-helium gas separation device according to claim 2, wherein: the hydrogen storage alloy and the heat conduction material are mixed, filled and layered and placed in the bed body.
5. The hydrogen-helium gas separation device according to claim 4, wherein: the heat conducting material comprises products such as wire mesh, foil and the like made of materials such as aluminum, copper, stainless steel and the like.
6. The hydrogen-helium gas separation device according to claim 4, wherein: the layered filling adopts a filter plate, a porous material, a honeycomb material and the like as materials of the partition layers, and hydrogen storage alloy is filled in each partition layer.
7. The hydrogen occluding alloy as recited in claim 2, wherein said alloy is AB5, AB2, AB-series hydrogen occluding alloy, including alloy composed of two or more of lanthanum, nickel, titanium, zirconium, cerium, cobalt, iron, aluminum, manganese, vanadium, yttrium, niobium, and molybdenum.
8. The hydrogen-helium gas separation device according to claim 2, wherein: coating the surface of the hydrogen storage alloy by physical vapor deposition or chemical method, wherein the coating material is Pd, ni, cu, co, ag, au, pt or Al 2 O 3 、SiO 2 One or more of the above components are compounded.
9. The hydrogen-helium gas separation device according to claim 2, wherein: the heat exchange structure can be one or more of a jacketed heat exchanger, a double-pipe heat exchanger, a coiled heat exchanger, a finned heat exchanger and a plate heat exchanger.
10. The hydrogen-helium gas separation device according to claim 1, wherein: the control system comprises a touch screen and a PLC control system.
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