CN113606494B - Device for producing different components of normal hydrogen and para hydrogen - Google Patents

Device for producing different components of normal hydrogen and para hydrogen Download PDF

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Publication number
CN113606494B
CN113606494B CN202110861632.7A CN202110861632A CN113606494B CN 113606494 B CN113606494 B CN 113606494B CN 202110861632 A CN202110861632 A CN 202110861632A CN 113606494 B CN113606494 B CN 113606494B
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hydrogen
normal
temperature
flow path
working medium
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CN113606494A (en
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陆小飞
张启勇
周芷伟
成安义
吴克平
李姗姗
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Hefei Institutes of Physical Science of CAS
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Hefei Institutes of Physical Science of CAS
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17D—PIPE-LINE SYSTEMS; PIPE-LINES
    • F17D1/00—Pipe-line systems
    • F17D1/02—Pipe-line systems for gases or vapours
    • F17D1/04—Pipe-line systems for gases or vapours for distribution of gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17D—PIPE-LINE SYSTEMS; PIPE-LINES
    • F17D3/00—Arrangements for supervising or controlling working operations
    • F17D3/01—Arrangements for supervising or controlling working operations for controlling, signalling, or supervising the conveyance of a product
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17D—PIPE-LINE SYSTEMS; PIPE-LINES
    • F17D5/00—Protection or supervision of installations
    • F17D5/005—Protection or supervision of installations of gas pipelines, e.g. alarm
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/34—Hydrogen distribution
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P90/00—Enabling technologies with a potential contribution to greenhouse gas [GHG] emissions mitigation
    • Y02P90/45—Hydrogen technologies in production processes

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  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Separation By Low-Temperature Treatments (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

The invention discloses a device for producing different components of normal hydrogen and para-hydrogen, wherein normal hydrogen in a room temperature state is divided into a normal temperature balanced hydrogen flow path, a primary balanced hydrogen flow path and a secondary balanced hydrogen flow path. The normal temperature equilibrium hydrogen flow path provides one path of normal temperature hydrogen, the first level normal hydrogen is provided after the temperature is reduced by the first level refrigerating medium, and the second level normal hydrogen is provided after the temperature is reduced by the second level refrigerating medium; the primary balance hydrogen flow path provides primary balance hydrogen through primary refrigeration working medium temperature reduction and normal secondary hydrogen catalytic conversion, and provides primary balance hydrogen with secondary temperature after the secondary refrigeration working medium temperature reduction; the secondary balance hydrogen flow path is used for producing primary balance hydrogen through the primary refrigeration working medium temperature reduction and the positive secondary hydrogen catalytic conversion, and then providing secondary balance hydrogen through the secondary refrigeration working medium temperature reduction and the positive secondary hydrogen catalytic conversion. The invention can provide the normal para-hydrogen fluid with different pressure, temperature, flow rate and composition ratio by adjusting the pressure and flow of three paths of normal hydrogen supply at room temperature.

Description

Device for producing different components of normal hydrogen and para hydrogen
Technical Field
The invention belongs to the technical field of industrial gas, and particularly relates to a device for producing different components of normal hydrogen and para-hydrogen.
Background
The hydrogen molecule is composed of two hydrogen atoms, and due to the difference in the spin direction of the two nuclei, there are two states of orthohydrogen and para-hydrogen. The spin isomers of these two hydrogens differ in that the two nuclei of orthohydrogen are in the same spin direction and the two nuclei of para-hydrogen are in opposite spin directions. When normal hydrogen is cooled to a lower temperature at room temperature, the normal hydrogen therein is slowly converted to para-hydrogen, resulting in a decrease in the proportion of the normal hydrogen component and an increase in the proportion of the para-hydrogen component and release of heat, and finally the components of the normal hydrogen and para-hydrogen reach a new equilibrium state.
The normal hydrogen takes equilibrium hydrogen at room temperature as a reference, and the components of the normal hydrogen and the para-hydrogen are basically unchanged in the rapid cooling or tempering process without catalytic conversion, namely, the components of the normal hydrogen and the para-hydrogen are 75% and 25%. The components of the equilibrium hydrogen are temperature dependent and are in an equilibrium state after the mutual conversion of the normal hydrogen and the para hydrogen is stable. Typically, the equilibrium hydrogen is 75% orthohydrogen+25% para-hydrogen at normal temperature, 50% orthohydrogen+50% para-hydrogen at 77K temperature, and 0.2% orthohydrogen+99.8% para-hydrogen at the normal boiling point (20.4K) of liquid hydrogen.
When the temperature of the equilibrium hydrogen changes, the natural conversion process between normal and para-hydrogen is extremely slow. The research result shows that the conversion between the orthohydrogen and the para-hydrogen is a magnetic mechanism, and the interaction of non-zero magnetic moment exists between a magnetic center and hydrogen atomic nuclei of two spins, so that the spin conversion of hydrogen molecules is accelerated. Therefore, a catalyst must be used to accelerate the catalytic conversion between normal hydrogen and para-hydrogen during the hydrogen cooling or heating process to reach equilibrium hydrogen in a new steady state.
The normal hydrogen and the para-hydrogen have different thermodynamic properties and characteristics, the conversion between the normal hydrogen and the para-hydrogen can generate heating or refrigerating effect, the normal hydrogen and the para-hydrogen with different components have wide application in engineering technology and scientific research, and normal-temperature hydrogen or low-temperature liquid hydrogen widely adopted in industry cannot provide normal para-hydrogen with any component ratio under different working conditions. The existing research on the para-hydrogen is focused on catalytic conversion devices (such as patents CN 203162532U, CN 203490203U, CN 108562112A and CN 109028755A), the performance of para-hydrogen catalysts and the measurement of para-hydrogen content (such as patent CN 104730141A), and the process is difficult to provide the para-hydrogen with different pressures, temperatures, flow rates and component proportions, so that the requirements of engineering technology and scientific research cannot be met.
Disclosure of Invention
In view of this, the present invention aims to provide an apparatus for producing different components of orthohydrogen and para-hydrogen in response to the hydrogen or liquid hydrogen demand of different components of orthohydrogen and para-hydrogen, which realizes the production of hydrogen or liquid hydrogen of different components of orthohydrogen and para-hydrogen by means of optimized mixing of hydrogen fluids of different components of orthohydrogen and para-hydrogen, and provides the orthopara-hydrogen fluids of different pressures, temperatures, flow rates and components in combination with the adjustment of the hydrogen supply pressure, flow rate and temperature.
In order to achieve the aim, the device for producing the normal hydrogen and the para-hydrogen with different components comprises a normal temperature balanced hydrogen flow path, a primary balanced hydrogen flow path, a secondary balanced hydrogen flow path, a primary refrigeration working medium flow path, a secondary refrigeration working medium flow path, a normal para-hydrogen output hydrogen flow path and a vacuum heat insulation cold box.
Further, the normal temperature balanced hydrogen flow path realizes the functions of normal temperature normal hydrogen, primary normal hydrogen and secondary normal hydrogen. The inlet end of the normal temperature balanced hydrogen flow path is connected with a hydrogen source, and is provided with a regulating valve and a flowmeter for controlling the flow rate of the normal temperature balanced hydrogen flow path. The outlet end of the normal temperature balanced hydrogen flow path is provided with three branches, a regulating valve and a thermometer thereof, wherein the first branch provides normal temperature hydrogen, the second branch provides normal hydrogen which is realized by cooling the first-stage refrigerating working medium, and the third branch provides normal hydrogen which is realized by cooling the second-stage refrigerating working medium.
Further, the primary balance hydrogen flow path realizes the primary balance hydrogen function of primary balance hydrogen and secondary temperature. The inlet end of the primary balance hydrogen flow path is connected with a hydrogen source and is provided with a regulating valve and a flowmeter for controlling the flow rate of the primary balance hydrogen flow path; the outlet end of the primary balance hydrogen flow path is provided with two branches, a regulating valve and a thermometer, the first branch provides primary balance hydrogen realized by a primary refrigeration working medium temperature reducing and positive secondary hydrogen catalytic converter, the second branch provides primary balance hydrogen with a secondary temperature realized by a secondary refrigeration working medium temperature reducing, and the positive secondary hydrogen component meter is arranged.
Further, the secondary balanced hydrogen flow path realizes the function of secondary balanced hydrogen. The inlet end of the secondary balanced hydrogen flow path is connected with a hydrogen source and is provided with a regulating valve and a flowmeter for controlling the flow rate of the secondary balanced hydrogen flow path, and the outlet end of the secondary temperature balanced hydrogen flow path is provided with a thermometer and a positive para-hydrogen component meter. The secondary balanced hydrogen flow path is to further realize secondary balanced hydrogen by the secondary refrigerant cooling and normal para-hydrogen catalytic converter with the primary balanced hydrogen realized by the primary refrigerant cooling and normal para-hydrogen catalytic converter.
Further, the primary refrigeration working medium flow path realizes the function of cooling the hydrogen flow path to the primary temperature. The inlet end of the primary refrigeration working medium flow path is provided with a primary refrigeration working medium input interface and a regulating valve, and the outlet end of the primary refrigeration working medium flow path is provided with a primary refrigeration working medium output regulating valve and an interface. The primary refrigeration working medium flow is used for providing cold energy by a low-temperature refrigerator or provided by a low-temperature working medium.
Further, the secondary refrigeration working medium flow path realizes the function of cooling the hydrogen flow path to the secondary temperature. The inlet end of the secondary refrigerant flow path is provided with a secondary refrigerant input interface and a regulating valve, and the outlet end of the secondary refrigerant flow path is provided with a secondary refrigerant output regulating valve and an interface. The secondary refrigeration working medium flow path provides cold energy by a low-temperature refrigerator or provides cold energy by a low-temperature working medium.
Further, the inlet end of the positive para-hydrogen output hydrogen flow path is provided with six paths of interfaces, and the positive para-hydrogen output hydrogen flow path is provided with a regulating valve, a heater, and pressure, temperature and positive para-hydrogen component meters; the outlet end of the positive para-hydrogen output hydrogen flow path provides output interfaces of hydrogen fluid outlet ends with different pressures, temperatures, flow rates and positive para-hydrogen component ratios.
Further, the six-way interface is respectively connected to the outlet ends of normal temperature normal hydrogen, primary normal hydrogen, secondary normal hydrogen, primary balanced hydrogen at secondary temperature and secondary balanced hydrogen. And selecting an optimal combination mode according to the temperature required by a user and the requirement of the normal para-hydrogen component so as to reduce the energy consumption of the device and the operation of the process.
Further, the hydrogen flow paths of the positive para-hydrogen with different components realize the functions of hydrogen fluids with different pressures, temperatures, flow rates and positive para-hydrogen component ratios. The hydrogen flow paths of the different-component normal-para-hydrogen are provided with normal-temperature balanced hydrogen flow paths, first-stage balanced hydrogen flow paths and interfaces of the outlet ends of the second-stage balanced hydrogen flow paths, the hydrogen flow paths of the different-component normal-para-hydrogen are provided with heaters and regulating valves, the hydrogen flow paths of the different-component normal-para-hydrogen are provided with pressure, temperature and component measuring meters, and the hydrogen flow paths of the different normal-hydrogen and para-hydrogen component ratios are provided with output interfaces. Further, the vacuum heat-insulating cold box has the functions of reducing the temperature of a hydrogen flow path to a specified temperature and performing normal para-hydrogen catalytic conversion. The vacuum heat-insulating cold box is provided with a primary refrigeration working medium precooling heat exchanger, a primary refrigeration working medium heat exchange module and a positive para-hydrogen catalytic converter, the vacuum heat-insulating cold box is provided with a secondary refrigeration working medium precooling heat exchanger, a secondary refrigeration working medium heat exchange module and a positive para-hydrogen catalytic converter, and the vacuum heat-insulating cold box is provided with a vacuum interface.
The working principle is as follows: a device for producing normal hydrogen and para-hydrogen with different components divides a normal hydrogen source in a room temperature state into three paths, wherein the first path of normal hydrogen source firstly provides one path of normal hydrogen (75% normal hydrogen+25% para-hydrogen), and is divided into two paths after being cooled to a first temperature by a first-stage refrigerating working medium, one path of normal hydrogen (75% normal hydrogen+25% para-hydrogen) is provided, and the other path of normal hydrogen is provided after being cooled to a second temperature by a second-stage refrigerating working medium, and is provided with second-stage normal hydrogen (75% normal hydrogen+25% para-hydrogen); the second path of normal hydrogen source is cooled to the first temperature through the first-stage refrigeration working medium and is used for producing first-stage balanced hydrogen through the normal-para-hydrogen catalytic converter, and then the first-stage balanced hydrogen is divided into two paths, wherein one path of normal hydrogen source is used for providing first-stage balanced hydrogen (for example, the first-stage temperature is 77K, 50 percent normal hydrogen and 50 percent para-hydrogen), and the other path of normal hydrogen source is used for providing second-stage balanced hydrogen after being cooled to the second-stage temperature through the second-stage refrigeration working medium (for example, the first-stage temperature is 77K, and 50 percent normal hydrogen and 50 percent para-hydrogen); the third normal hydrogen source is cooled to the first temperature through the first-stage refrigerant and produces first-stage balanced hydrogen through the normal-para-hydrogen catalytic converter, and then cooled to the second temperature through the second-stage refrigerant and produces second-stage balanced hydrogen (taking the second temperature of 20K as an example, 0.02% normal hydrogen+99.8% para-hydrogen) through the normal-para-hydrogen catalytic converter. The invention realizes the production of hydrogen or liquid hydrogen of different components of normal hydrogen by adjusting the supply pressure and flow rate of three paths of normal hydrogen at room temperature and by adopting a mode of optimizing and combining six paths of normal hydrogen at room temperature, primary normal hydrogen, primary balanced hydrogen, secondary normal hydrogen, primary balanced hydrogen at secondary temperature and secondary balanced hydrogen.
The invention has the following beneficial effects:
the refrigeration working medium and the normal-para-hydrogen catalytic converter adopted by the invention are mature, and the designed technological process can be flexibly operated according to the requirements to realize the high-efficiency production of hydrogen or liquid hydrogen with different normal hydrogen and para-hydrogen component ratios. The device for producing the normal hydrogen and the para-hydrogen with different components can provide normal para-hydrogen fluid with different pressures, temperatures, flow rates and component proportions, meets the requirements of engineering application and scientific research on normal para-hydrogen with different working conditions, and has comprehensive functions and strong applicability.
Drawings
FIG. 1 is a process diagram of the present invention.
In the figure, J1, J4-J8-device interfaces, J9-vacuum pump interfaces, CB-vacuum heat insulation cold boxes, OP 1-OP 3-normal para-hydrogen catalytic converters, HX 1-primary heat exchangers, HX 2-secondary heat exchangers, H1-H6-heat exchangers, R1-primary refrigerant heat exchange units, R2-secondary refrigerant heat exchange units and V H2 、V R1 、V R2 、V 10 、V 11 、V 12 、V 13 、V 20 、V 22 、V 23 、V 30 、V 40 、V 60 、V 80 -regulating valve, P 0 ～P 2 、P 4 -pressure gauges, T1, T2, T4, T11, T13, T21, T23, T31, T33-thermometers, Q-heaters, F1-F3-flowmeters, A1-A4-n-para-hydrogen component meters, 1, 10-12, 20-22, 30, 31, 40-46, 48, 50, 60, 70, 80-conduits, L1, L2-level gauges.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the present invention will be described in further detail below with reference to the embodiments of the present invention and the accompanying drawings, but the described embodiments are some, but not all, embodiments of the present invention. Other embodiments that are not creatively labor by those of ordinary skill in the art based on the embodiments of the present invention are all within the protection scope of the present invention.
As shown in fig. 1, an apparatus for producing different components of ortho-hydrogen and para-hydrogen is disclosed, which comprises the following specific components: a normal temperature balanced hydrogen flow path, a primary balanced hydrogen flow path, a secondary balanced hydrogen flow path, a primary refrigerant flow path, a secondary refrigerant flow path, a normal secondary hydrogen output hydrogen flow path and a vacuum heat insulation cold box.
Specifically, an apparatus for producing different components in terms of the ratio of normal hydrogen to para-hydrogen includes the following embodiments (taking a primary temperature of 77K, a secondary temperature of 20K as an example):
the apparatus used in the device is as follows, with reference to fig. 1. Normal hydrogen in room temperature state passes through device interface J1 and regulating valve V H2 Is connected to a pipe 1, the pipe 1 is provided with a pressure gauge P0 and passes through a regulating valve V H2 And the control device supplies air pressure. The outlet of the pipeline 1 is divided into three paths, and the first path is provided with a flowmeter F1 and passes through a regulating valve V 10 Connected to the normal temperature hydrogen-balancing flow path pipe 10, the second path is provided with a flow meter F2 and passes through a regulating valve V 20 Connected to the primary balance hydrogen flow path pipe 20, the third path is provided with a flow meter F3 and passes through a regulating valve V 30 Is connected to the secondary balance hydrogen flow path conduit 30.
The normal temperature balanced hydrogen flow path pipeline 10 realizes the functions of providing normal temperature normal hydrogen, primary normal hydrogen and secondary normal hydrogen; the normal temperature balanced hydrogen flow path pipeline 10 is divided into two paths after entering the vacuum heat insulation cold box CB, and one path passes through the regulating valve V 11 The other path is connected to the pipeline 11 after being precooled by the primary heat exchanger HX1 and the temperature of the primary refrigerant heat exchange unit R1 is reduced, wherein normal hydrogen (75% normal hydrogen+25% secondary hydrogen) at normal temperature is provided by the pipeline 41. The pipe 11 is provided with a thermometer T11 and a normal para-hydrogen component meter A1. The outlet of the pipeline 11 is divided into two paths, one path passes through the regulating valve V 12 Is connected to line 42 to provide primary normal hydrogen (75% normal hydrogen +25% para-hydrogen) and the other is passed through regulator valve V 13 Is connected to the pipe 12. The pipeline 12 is connected to the pipeline 44 after passing through the secondary heat exchanger HX2 and the secondary refrigeration medium heat exchange unit for cooling. Conduit 44 is provided with thermometer T13 and provides secondary normal hydrogen (75% normal hydrogen +25% para-hydrogen). The outlets of the piping 41, the piping 42, and the piping 44 are connected to the normal-para-hydrogen output hydrogen flow path piping 40.
The primary balance hydrogen flow path pipe 20 realizes a primary balance hydrogen function of providing primary balance hydrogen and secondary temperature; the primary balance hydrogen flow path pipeline 20 enters the vacuum heat insulation cold box CB, is precooled by the primary heat exchanger HX1, is cooled by the primary refrigeration working medium heat exchange R1, and is connected to the pipeline 21 by the primary-secondary hydrogen catalytic converter OP 1. The pipe 21 is provided with a thermometer T21 and a normal para-hydrogen component meter A2. The outlet of the pipeline 21 is divided into two paths, one path passes through the regulating valve V 22 Connection to conduit 43 provides primary balanceHydrogen (50% orthohydrogen +50% para-hydrogen), the other way through regulating valve V 23 Is connected to the pipe 22. Conduit 22 is connected to conduit 45 via secondary heat exchanger HX2 pre-cooling and secondary refrigerant heat exchange unit R2. Conduit 45 is provided with a thermometer T23 and provides primary balance hydrogen (50% orthohydrogen +50% para-hydrogen) at the secondary temperature. Outlets of the pipes 43 and 45 are connected to the normal-para-hydrogen output hydrogen flow path pipe 40
The secondary balance hydrogen flow path pipe 30 performs a function of providing secondary balance hydrogen; the secondary balance hydrogen flow path pipeline 30 enters the vacuum heat insulation cold box CB, is precooled by the primary heat exchanger HX1, is cooled by the primary refrigeration working medium heat exchange unit R1, and is connected to the pipeline 31 by the normal para-hydrogen catalytic converter OP 2. The pipe 31 is provided with a thermometer T31, and is connected to the pipe 46 through a secondary heat exchanger HX2 precooling and secondary refrigeration working medium heat exchange unit R2 cooling and an orthopara-hydrogen catalytic converter OP 3. Conduit 46 is provided with thermometer T33 and a positive para-hydrogen component meter A3 and provides secondary equilibrium hydrogen (0.02% positive hydrogen +99.8% para-hydrogen). The outlet of the pipe 46 is connected to the normal-para-hydrogen output hydrogen flow path pipe 40.
The normal-para-hydrogen output hydrogen flow path pipeline 40 realizes the function of producing hydrogen or liquid hydrogen of normal-para-hydrogen with different components in a mode of mixing normal-temperature normal hydrogen, primary balanced hydrogen, secondary normal hydrogen, primary balanced hydrogen with secondary temperature and secondary balanced hydrogen; the positive para-hydrogen output hydrogen flow path pipeline 40 is provided with a heater Q and a thermometer T4 to realize the temperature regulation of the positive para-hydrogen fluid; the normal-para-hydrogen output hydrogen flow path pipeline 40 is provided with a regulating valve V 40 Is connected to conduit 48 to effect pressure regulation of the normal para-hydrogen; the pipe 48 is provided with a pressure gauge P4 and a normal para-hydrogen component gauge A4; the outlet of the normal-para-hydrogen output hydrogen flow path pipe 48 is connected to the device interface J4, and the normal-para-hydrogen output hydrogen flow path pipe 48 employs a vacuum insulation pipe.
The primary refrigeration working medium heat exchange unit R1 has the function of providing a cold source for cooling normal-temperature hydrogen to primary temperature; the primary refrigerant heat exchange unit R1 is provided with a pipeline 50 of a primary refrigerant inlet and a pipeline 60 of an outlet, the primary refrigerant heat exchange unit R1 is provided with a heat exchanger H1, a heat exchanger H2 and a heat exchanger H3 of a heat flow path, and the primary refrigerant is cooledThe working medium heat exchange unit R1 is provided with a pressure gauge P1, a thermometer T1 and a liquid level gauge L1. The inlet end of the pipeline 50 passes through a regulating valve V R1 To the device interface J5, the tubing 50 employs vacuum insulated tubing. The outlet of the pipeline 60 of the primary refrigeration working medium outlet passes through the regulating valve V 60 To the device interface J6.
The secondary refrigeration working medium heat exchange unit R2 provides a cold source for cooling the primary temperature hydrogen to the secondary temperature; the secondary refrigerant heat exchange unit R2 is provided with a pipeline 70 of a secondary refrigerant inlet and a pipeline 80 of an outlet, the secondary refrigerant heat exchange unit R2 is provided with a heat exchanger H4, a heat exchanger H5 and a heat exchanger H6 of a heat flow path, and the secondary refrigerant heat exchange unit R2 is provided with a pressure gauge P2, a thermometer T2 and a liquid level gauge L2. The inlet end of the pipeline 70 passes through a regulating valve V R2 To the device interface J7, the pipe 70 employs a vacuum insulated pipe. The outlet of the pipeline 80 of the secondary refrigeration working medium outlet passes through the regulating valve V 80 To the device interface J8.
The vacuum heat-insulating cold box CB provides the function of low-temperature heat-insulating environment of the device; the vacuum heat-insulating cold box CB is provided with a vacuum pump interface J9, and the vacuum degree is required to be not higher than 10 during normal operation -3 Pa。
The working process of the system is as follows:
taking 77K primary temperature and 50% orthohydrogen plus 50% para-hydrogen as primary balance hydrogen components, 20K secondary temperature and 0.02% orthohydrogen plus 99.8% para-hydrogen as secondary balance hydrogen components as examples, the specific process for obtaining the typical working condition orthopara-hydrogen fluid is as follows:
typical working condition 1, 25% -50% secondary hydrogen production operation of primary temperature: opening the regulating valve V H2 And the pressure gauge P0 is controlled to be a set value according to the requirement, and the first-stage refrigerating medium inlet valve regulating valve V is opened R1 And an outlet valve V 60 And the temperature T1, the pressure P1 and the liquid level L1 of R1 (if applicable) are controlled at the set values. Opening the regulating valve V 10 And V 12 And closing V 11 And V 13 Primary normal hydrogen (25% para-hydrogen) is provided through line 42 and regulating valve V is opened 20 And V 22 And closing V 23 Provided by a pipe 43Primary equilibrium hydrogen (50% para-hydrogen). According to the ratio of the para-hydrogen to the para-hydrogen, through a regulating valve V 10 The flow rate F1 of the normal temperature balance hydrogen flow path 10 is regulated by a regulating valve V 20 The flow rate F2 of the primary balance hydrogen flow path 20 is adjusted, and the adjusting valve V is further finely adjusted by the result of the positive parahydrogen component tester A4 12 And V 22 Realizes the production of 25 to 50 percent of secondary hydrogen at the primary temperature.
Typical working condition 2, production operation of 50% -99.8% parahydrogen of primary temperature: opening the regulating valve V H2 And the pressure gauge P0 is controlled to be a set value according to the requirement, and the first-stage refrigerating medium inlet valve regulating valve V is opened R1 And an outlet valve V 60 And controls the temperature T1, the pressure P1, and the liquid level L1 of R1 at set values. Opening the regulating valve V of the two-stage refrigerating medium inlet valve R2 And an outlet valve V 80 And controls the temperature T2, pressure P2 and level L2 of R2 (as applicable) at the set values. Opening the regulating valve V 20 And V 22 And closing V 23 Primary balance hydrogen (50% para-hydrogen) is provided through line 43 and regulating valve V is opened 30 Secondary balance hydrogen (99.8% para-hydrogen) is provided through line 46. According to the ratio of the para-hydrogen to the para-hydrogen, through a regulating valve V 20 The flow rate F2 of the normal temperature balance hydrogen flow path 20 is regulated by a regulating valve V 30 The flow rate F3 of the primary balance hydrogen flow path 30 is adjusted, and the adjusting valve V is further finely adjusted by the result of the positive parahydrogen component tester A4 22 Realizes the production of 50 to 99.8 percent of parahydrogen at the primary temperature.
Typical working condition 3, 25% -50% secondary hydrogen production operation of secondary temperature: opening the regulating valve V H2 And the pressure gauge P0 is controlled to be a set value according to the requirement, and the first-stage refrigerating medium inlet valve regulating valve V is opened R1 And an outlet valve V 60 And the temperature T1, the pressure P1 and the liquid level L1 of the R1 are controlled to be set values, and a second-stage refrigerating medium inlet valve regulating valve V is opened R2 And an outlet valve V 80 And controls the temperature T2, pressure P2 and level L2 of R2 (as applicable) at the set values. Opening the regulating valve V 10 And V 13 And closing V 11 And V 12 Primary normal hydrogen (25% para-hydrogen) at secondary temperature is provided through line 44 and regulating valve V is opened 20 And V 23 And closingClosed V 22 Primary balance hydrogen (50% para-hydrogen) at secondary temperature is provided through line 45. According to the ratio of the para-hydrogen to the para-hydrogen, through a regulating valve V 10 The flow rate F1 of the normal temperature balance hydrogen flow path 10 is regulated by a regulating valve V 20 The flow rate F2 of the primary balance hydrogen flow path 20 is adjusted, and the adjusting valve V is further finely adjusted by the result of the positive parahydrogen component tester A4 13 And V 23 Realizing the production of 25 to 50 percent of secondary hydrogen at the second-stage temperature.
Typical working condition 4, production operation of 50% -99.8% para-hydrogen of secondary temperature: opening the regulating valve V H2 And the pressure gauge P0 is controlled to be a set value according to the requirement, and the first-stage refrigerating medium inlet valve regulating valve V is opened R1 And an outlet valve V 60 And the temperature T1, the pressure P1 and the liquid level L1 of the R1 are controlled to be set values, and a second-stage refrigerating medium inlet valve regulating valve V is opened R2 And an outlet valve V 80 And controls the temperature T2, pressure P2 and level L2 of R2 (as applicable) at the set values. Opening the regulating valve V 20 And V 23 And closing V 22 Primary balance hydrogen (50% para-hydrogen) at secondary temperature is provided through line 45 and regulating valve V is opened 30 Secondary balance hydrogen (containing 99.8 para-hydrogen) is provided through line 46. According to the ratio of the para-hydrogen to the para-hydrogen, through a regulating valve V 20 The flow rate F2 of the normal temperature balance hydrogen flow path 20 is regulated by a regulating valve V 30 The flow rate F3 of the secondary balance hydrogen flow path 30 is adjusted, and the adjusting valve V is further finely adjusted by the result of the positive parahydrogen component tester A4 23 Realizing the production of 50 to 99.8 percent of secondary hydrogen at the second-stage temperature.
Normal para-hydrogen production operation outside typical operating conditions: typical working conditions 1-4 can realize the production of 25% -99.8% continuous para-hydrogen components. In addition, the temperature of the normal para-hydrogen fluid outside the typical working condition can be continuously regulated by controlling the temperature of T4 through opening the heater Q, and the temperature of the para-hydrogen fluid is continuously regulated through the regulating valve V 40 The pressure of the P4 is controlled to realize continuous adjustment of the pressure of the normal para-hydrogen fluid.
The primary temperature and the secondary temperature given in the specific embodiment above can be realized by adopting corresponding refrigeration working media or a cryocooler according to the requirements of different components of the orthohydrogen and the para-hydrogen.
In summary, the embodiment of the invention can realize the production of different components of normal hydrogen and para-hydrogen, and the provided six paths of typical temperature and the fluid with the normal para-hydrogen component ratio can select a proper combination mode according to the requirements so as to reduce the energy consumption of the device or reduce the flow operation, thereby meeting the requirements of engineering application and scientific research on normal para-hydrogen with different working conditions.
In summary, the above embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (1)

1. An apparatus for producing different components of normal and para-hydrogen, characterized in that: the device comprises a normal temperature balanced hydrogen flow path, a primary balanced hydrogen flow path, a secondary balanced hydrogen flow path, a primary refrigeration working medium flow path, a secondary refrigeration working medium flow path, a normal secondary hydrogen output hydrogen flow path and a vacuum heat insulation cold box;
the inlet end of the normal temperature balanced hydrogen flow path is connected with a hydrogen source and is provided with a regulating valve and a flowmeter for controlling the flow rate of the normal temperature balanced hydrogen flow path; the outlet end of the normal temperature balanced hydrogen flow path is provided with three branches, a regulating valve and a thermometer thereof, wherein the first branch provides normal temperature hydrogen, the second branch provides first-level normal hydrogen realized by cooling the first-level refrigeration working medium, and the third branch provides second-level normal hydrogen realized by cooling the second-level refrigeration working medium;
the inlet end of the primary balance hydrogen flow path is connected with a hydrogen source and is provided with a regulating valve and a flowmeter for controlling the flow rate of the primary balance hydrogen flow path; the outlet end of the primary balance hydrogen flow path is provided with two branches, a regulating valve and a thermometer thereof, the first branch provides primary balance hydrogen realized by a primary refrigeration working medium temperature reducing and normal-secondary hydrogen catalytic converter and is provided with a normal-secondary hydrogen component meter, and the second branch provides primary balance hydrogen at a secondary temperature realized by a secondary refrigeration working medium temperature reducing;
the inlet end of the secondary balance hydrogen flow path is connected with a hydrogen source and is provided with a regulating valve and a flowmeter for controlling the flow rate of the secondary balance hydrogen flow path; the outlet end of the secondary balance hydrogen flow path is provided with a thermometer and a positive secondary hydrogen component meter, and the outlet end of the secondary balance hydrogen flow path provides secondary balance hydrogen realized by a primary refrigeration working medium and a secondary refrigeration working medium and a positive secondary hydrogen catalytic converter;
the inlet end of the primary refrigeration working medium flow path is provided with a primary refrigeration working medium input interface and a regulating valve, the outlet end of the primary refrigeration working medium flow path is provided with a primary refrigeration working medium output interface and a regulating valve, and the primary refrigeration working medium flow path provides cold energy by a low-temperature refrigerator or provides cold energy by a low-temperature working medium;
the inlet end of the secondary refrigerant flow path is provided with a secondary refrigerant input interface and a regulating valve, the outlet end of the secondary refrigerant flow path is provided with a secondary refrigerant output interface and a regulating valve, and the secondary refrigerant flow path provides cold energy by a low-temperature refrigerator or provides cold energy by a low-temperature refrigerant;
the inlet end of the positive para-hydrogen output hydrogen flow path is provided with six paths of interfaces, and the positive para-hydrogen output hydrogen flow path is provided with a regulating valve, a heater, and pressure, temperature and positive para-hydrogen component meters; the outlet end of the positive para-hydrogen output hydrogen flow path provides output interfaces of hydrogen fluid outlet ends with different pressures, temperatures, flow rates and positive para-hydrogen component ratios;
the six-way interface is respectively connected to the normal temperature normal hydrogen, the first-stage normal hydrogen, the second-stage normal hydrogen, the first-stage balanced hydrogen and the outlet end of the second-stage balanced hydrogen;
the vacuum heat-insulating cold box is provided with a primary refrigeration working medium precooling heat exchanger, a primary refrigeration working medium heat exchange unit and a positive para-hydrogen catalytic converter, the vacuum heat-insulating cold box is provided with a secondary refrigeration working medium precooling heat exchanger, a secondary refrigeration working medium heat exchange unit and a positive para-hydrogen catalytic converter, and the vacuum heat-insulating cold box is provided with a vacuum interface;
the device for producing the normal hydrogen and the para-hydrogen with different components divides a normal hydrogen source in a room temperature state into three paths, wherein the first path of normal hydrogen source firstly provides one path of normal hydrogen at normal temperature, and is divided into two paths after being cooled to a first temperature by a first-stage refrigeration working medium, one path of normal hydrogen is provided, and the other path of normal hydrogen is provided after being cooled to a second temperature by a second-stage refrigeration working medium; the second path of normal hydrogen source is cooled to the first temperature through the first-stage refrigeration working medium and is used for producing first-stage balanced hydrogen through the normal-secondary hydrogen catalytic converter, and then the second path of normal hydrogen source is divided into two paths, wherein one path of normal hydrogen source is used for providing the first-stage balanced hydrogen, and the other path of normal hydrogen source is used for providing the first-stage balanced hydrogen at the second temperature after being cooled to the second temperature through the second-stage refrigeration working medium; the third path of normal hydrogen source is cooled to the first temperature through the first-stage refrigeration working medium and produces first-stage balanced hydrogen through the positive-secondary hydrogen catalytic converter, and then cooled to the second temperature through the second-stage refrigeration working medium and produces second-stage balanced hydrogen through the positive-secondary hydrogen catalytic converter; the hydrogen or liquid hydrogen production of the normal secondary hydrogen with different components is realized by adjusting the supply pressure and the flow rate of three paths of normal hydrogen at room temperature and by adopting a mode of optimizing and combining six paths of normal hydrogen at room temperature, primary normal hydrogen, primary balanced hydrogen, secondary normal hydrogen, primary balanced hydrogen at secondary temperature and secondary balanced hydrogen.
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