CN113491947A - Stable isotope gas separation method and apparatus - Google Patents
Stable isotope gas separation method and apparatus Download PDFInfo
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- CN113491947A CN113491947A CN202010198095.8A CN202010198095A CN113491947A CN 113491947 A CN113491947 A CN 113491947A CN 202010198095 A CN202010198095 A CN 202010198095A CN 113491947 A CN113491947 A CN 113491947A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D59/00—Separation of different isotopes of the same chemical element
- B01D59/22—Separation by extracting
- B01D59/26—Separation by extracting by sorption, i.e. absorption, adsorption, persorption
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Of Gases By Adsorption (AREA)
Abstract
The application discloses a stable isotope gas separation method and device, and relates to the technical field of material analysis and detection. The stable isotope gas separation method comprises the following steps: a) contacting the mixed gas containing the raw material gas with an adsorbing material for adsorption; wherein the raw material gas contains target isotope gas; b) heating to obtain desorption gas; wherein the desorption gas contains the target isotope gas; the target isotope gas is a stable isotope gas. The stable isotope gas separation method is simple in separation process, can obtain high-abundance stable isotope products, and can be suitable for large-scale production of stable isotope gas.
Description
Technical Field
The application relates to the technical field of material analysis and detection, and particularly discloses a stable isotope gas separation method and a stable isotope gas separation device.
Background
Isotopes are species of the same number of protons and different numbers of neutrons in the nucleus, among which radioactive isotopes are called "radioisotopes (unstable)", which are not radioactive and have a half-life greater than 1015The year is called "stable isotope". With the development of scientific technology and material analysis and detection technology, stable isotopes have more and more prominent importance in the fields of industry, agriculture and medicine, biology, national defense industry and the like, and the demand for stable isotopes urgently promotes the continuous improvement and development of stable isotope separation technology.
In the related art, the separation methods of stable isotopes include an electrolysis method, a rectification method, a double-temperature exchange method, a chemical exchange method, a low-temperature rectification method, a thermal diffusion method, an ion exchange resin method, a laser separation method, an electromagnetic method and the like, but compared with the low-temperature rectification method and the chemical exchange rectification method which are currently applied to industrial production, the separation methods of the stable isotopes have the disadvantages of large energy consumption and high cost in industrial application, and limit the preparation of high-abundance stable isotope products. Therefore, there is a need to research and explore a method with higher efficiency, convenient separation operation and low cost to realize the industrial scale production of high-abundance stable isotope products.
Disclosure of Invention
According to one aspect of the application, a stable isotope gas separation method and a stable isotope gas separation device are provided, and the problems of low abundance of stable isotope gas, large difficulty in industrial large-scale production and the like in the related technology are solved at least to a certain extent.
According to an aspect of the present application, there is provided a stable isotope gas separation method including:
a) contacting the mixed gas containing the raw material gas with an adsorbing material for adsorption;
wherein the raw material gas contains target isotope gas;
b) heating to obtain desorption gas;
wherein the desorption gas contains the target isotope gas;
the target isotope gas is a stable isotope gas.
Optionally, the adsorbent material is a molecular sieve;
alternatively, the molecular sieve is selected from any of Na-type molecular sieves (4A,13X), Ca-type molecular sieves (5A,10X) or modified molecular sieves.
Optionally, the stable isotope gas contains a stable isotope selected from the group consisting of10B、13C、15And N.
Optionally, the stable isotope is10B, the stable isotope gas is10B2H6(ii) a Or the like, or a combination thereof,
the stable isotope is13C, the stable isotope gas is selected from13CO、13CO2、13CH4Any one of (a); alternatively, the first and second electrodes may be,
the stable isotope is15N, the stable isotope gas is selected from15NO、15NH3Any one of the above.
Optionally, the stable isotope gas is10B2H6The adsorption temperature is-40 to-140 ℃; or the like, or a combination thereof,
the stable isotope gas is13CO, the adsorption temperature is-150 to-200 ℃; alternatively, the first and second electrodes may be,
the stable isotope gas is13CO2The adsorption temperature is-30 to-130 ℃; alternatively, the first and second electrodes may be,
the stable isotope gas is13CH4The adsorption temperature is-110 to-200 ℃; alternatively, the first and second electrodes may be,
the stable isotope gas is15NO, the adsorption temperature is-100 to-200 ℃; alternatively, the first and second electrodes may be,
the stable isotope gas is15NH3The adsorption temperature is-20 to-80 ℃.
Alternatively, the present application may be used to isolate stable isotopes10B、13C、15The gas of N is not particularly limited, and a gas containing other stable isotopes may be separated.
Optionally, the heating rate is 2-10 ℃/min;
the lower limit of the temperature rising rate is independently selected from 2 ℃/min, 4 ℃/min, 5 ℃/min, 7 ℃/min and 9 ℃/min;
the upper limit of the temperature rise rate is independently selected from 3 ℃/min, 5 ℃/min, 6 ℃/min, 8 ℃/min and 10 ℃/min.
In some possible embodiments, in the process of performing stable isotope gas separation, when a multi-stage cascade of chromatographic columns is used, the multi-stage chromatographic columns may be heated at the same heating rate when heated; in some possible embodiments, the temperature of the multiple stages of chromatography columns may be raised at different temperature raising rates, for example, for three stages of cascaded chromatography columns, the temperature raising rate from the first stage to the third stage is sequentially increased or sequentially decreased, based on which the temperature or temperature raising rate of each stage of chromatography column may be dynamically adjusted, respectively, without affecting the temperature of other chromatography columns, and the flexibility of the separation process is improved while ensuring the temperature stability of other chromatography columns.
Optionally, the desorption conditions are: the desorption temperature is 500-600 ℃;
the lower limit of the desorption temperature is independently selected from: 500 ℃, 520 ℃, 550 ℃, 580 ℃ and 590 ℃;
the upper limit of the desorption temperature is independently selected from: 520 ℃, 550 ℃, 580 ℃, 590 ℃ and 600 ℃;
preferably, the stable isotope gas is10B2H6The desorption temperature is 500-600 ℃; or the like, or a combination thereof,
the stable isotope gas is13CO desorption temperature is 500-580 ℃; alternatively, the first and second electrodes may be,
the stable isotope gas is13CO2The desorption temperature is 550-600 ℃; alternatively, the first and second electrodes may be,
the stable isotope gas is13CH4The desorption temperature is 500-600 ℃; alternatively, the first and second electrodes may be,
the stable isotope gas is15The desorption temperature of NO is 500-550 ℃; alternatively, the first and second electrodes may be,
the stable isotope gas is15NH3The desorption temperature is 500-550 ℃.
Optionally, the raw material gas further contains a non-target isotope gas;
the non-target isotope gas contains a non-target isotope;
the non-target isotope and the target isotope are different isotopes of the same element.
Alternatively, the non-target isotope gas may be a gas containing an isotope of carbon monoxide and carbon monoxideThe target isotope gas has a radioisotope gas of the same element, for example,13the radioisotope of C is14C, etc.;
alternatively, the non-target isotope may also include a stable isotope gas having the same element as the target isotope gas, for example12C、14N、11B, and the like.
Optionally, the mixed gas further contains a carrier gas;
optionally, the molar ratio of the raw material gas to the carrier gas in the mixed gas is 1: 1-1: 3;
the molar ratio of the raw material gas to the carrier gas in the mixed gas is independently selected from 1:1, 1:1.2, 1:1.4, 1:2, 1:2.4, 1:2.6 and 1: 3.
Optionally, the carrier gas is selected from any one of inert gases;
the inert gas comprises helium and argon;
preferably, helium is used as the carrier gas.
Optionally, the flow of the carrier gas is 0.2-1L/min;
the flow of the carrier gas is independently selected from 0.2L/min, 0.4L/min, 0.5L/min, 0.8L/min and 1L/min.
Optionally, the inlet pressure of the raw material gas is 0.1-0.3 Mpa;
the lower limit of the gas inlet pressure of the raw material gas is independently selected from 0.1Mpa, 0.12Mpa, 0.15Mpa, 0.2Mpa and 0.25 Mpa;
the upper limit of the inlet pressure of the raw material gas is independently selected from 0.12Mpa, 0.15Mpa, 0.2Mpa, 0.25Mpa and 0.3 Mpa.
Optionally, if the adsorption temperature is lower than the preset temperature, a liquid nitrogen refrigerator is used for cooling;
if the adsorption temperature is greater than or equal to the preset temperature, a mechanical refrigerator is adopted for cooling;
preferably, the preset temperature is-50 to-20 ℃.
The preset temperature is determined according to the target isotope gas to be separated and the cooling capacity of a cooling mode; for example, if the adsorption temperature of the target isotope gas to be separated is-198 ℃, the liquid nitrogen refrigerator and the mechanical refrigerator are used for cooling, and after the temperature is lower than-50 ℃, the mechanical refrigerator cannot supply the cold at the temperature, the liquid nitrogen refrigerator is used for cooling, so that the use amount of liquid nitrogen is reduced under the condition of ensuring the normal operation of the refrigerator, and the separation energy consumption is reduced.
Optionally, prior to the adsorption process, the method further comprises: activating the chromatographic column filled with the adsorption material at the activation temperature of 200-300 ℃;
the lower limit of the activation temperature is independently selected from: 200 ℃, 220 ℃, 240 ℃, 260 ℃ and 280 ℃;
the upper limit of the activation temperature is independently selected from: 220 deg.C, 240 deg.C, 260 deg.C, 280 deg.C, 300 deg.C.
In some possible embodiments, the column is heated to an activation temperature and purified helium is passed through the column to activate the column.
Alternatively, the content of the target isotope gas in the finally obtained desorbed gas is 90% by mass or more.
According to one aspect of the present application, there is provided a stable isotope gas separation apparatus, the apparatus including a chromatography column unit, a cooling unit, a temperature measurement component, and a control unit;
the temperature measuring component is used for measuring the temperature of the chromatographic column unit;
the cooling unit is used for cooling the chromatographic column unit;
the control unit is respectively electrically connected with the temperature measuring component and the cooling unit and is used for controlling the temperature of the chromatographic column unit according to the temperature measured by the temperature measuring component;
the control unit supplies cold to the chromatographic column unit by switching the composite cold supply unit to different refrigeration modes.
Optionally, the apparatus further comprises:
the gas distribution and purification unit is positioned at the gas inlet end of the chromatographic column unit and is used for providing a raw gas of the mixed gas for the chromatographic column unit;
a carrier gas supply unit, which is positioned at the gas inlet end of the chromatographic column unit and is used for providing a carrier in the mixed gas and driving the mixed gas in the chromatographic column unit to flow;
wherein, the control unit is respectively connected with the gas distribution and purification unit and the carrier gas supply system electric unit.
Optionally, the apparatus further comprises:
a pressure measuring means for measuring the pressure of the gas within the device;
and the mass flow meter is positioned in the carrier gas supply unit and used for measuring the flow of the carrier gas in the carrier gas supply unit.
Optionally, the device further comprises a gas flow path and a liquid flow path;
the gas flow path comprises gas connecting pipelines of all units in the device, and the liquid flow path is used for circulating flow and collection of liquid in the device;
wherein, the air flow path and the liquid flow path both comprise a mass flow meter, a pressure measuring component and a vacuum component.
Optionally, the cooling unit is a combined cooling unit for cooling by a liquid nitrogen refrigerator and a mechanical refrigerator;
the control unit is also used for switching the refrigeration mode of the composite cold supply unit according to the temperature measured by the temperature measuring component;
optionally, if the current adsorption temperature of the device is lower than the preset temperature, a liquid nitrogen refrigerating machine is adopted for cooling;
if the adsorption temperature is greater than or equal to the preset temperature, a mechanical refrigerator is adopted for cooling;
preferably, the preset temperature is-50 ℃.
Optionally, the column unit comprises one or more cascaded columns packed with molecular sieves;
wherein the chromatographic column unit is immersed in a containment means containing a coolant;
optionally, the coolant is selected from any one of liquid nitrogen and liquid ammonia.
Optionally, the chromatography column unit comprises a three-stage cascade of chromatography columns, wherein:
the outer diameter of the first-stage chromatographic column is 0.34-0.4 inch;
the outer diameter of the second-stage chromatographic column is 0.2-0.3 inch;
the column outer diameter of the third-stage chromatographic column is 0.1-0.15 inch;
wherein the packing density of the molecular sieve in any chromatographic column is 0.5-0.7 g/mL;
the packing density of the molecular sieve in any chromatographic column is independently selected from the group consisting of: 0.5g/mL, 0.55g/mL, 0.6g/mL, 0.65g/mL, 0.7 g/mL.
It should be noted that, in the process of performing stable isotope gas separation, the temperature rise rates of the first-stage chromatography column, the second-stage chromatography column and the third-stage chromatography column may be the same or different, for example, for a three-stage cascade chromatography column, the temperature rise rates from the first stage to the third stage are sequentially increased or sequentially decreased, based on which, the temperature or the temperature rise rate of each stage of chromatography column can be dynamically adjusted, without affecting the temperatures of other chromatography columns, and the flexibility of the separation process is improved while ensuring the stability of the temperatures of other chromatography columns. .
Optionally, the apparatus of the present application may further comprise an analytical measurement unit, including a chromatograph, a mass spectrometer, or the like, for detection analysis of the stable isotope gas.
The stable isotope gas separation method has the following beneficial effects:
after the mixed gas containing the target isotope gas is adsorbed by the adsorbing material, the target isotope gas is desorbed under the condition of temperature rise to obtain the stable isotope gas. Different isotope gases are desorbed from the adsorbing material successively at different desorption temperatures so as to achieve the purpose of separating stable isotope gases, the process is simple, the operation is simple and convenient, high-abundance stable isotope gases can be obtained, and the method is suitable for industrial large-scale production of stable isotope gas products;
furthermore, the adsorption material is a molecular sieve, so that the service life is long, the adsorption material can be regenerated and reused after being activated, and the separation cost is reduced; the raw material gas also contains non-target isotope gas, the non-target isotope and the target isotope are different isotopes of the same element, and stable isotope gas can be separated from different isotope gas of the same element based on the method;
further, the mixed gas also comprises carrier gas, and the carrier gas drives the raw material gas, so that the gas retention can be reduced, the separation effect can be improved, and a high-abundance stable isotope gas product can be obtained;
furthermore, the separation method can switch different cooling modes in different temperature intervals, energy consumption is low, and cooling cost is reduced.
The stable isotope gas separation device has the following beneficial effects:
according to the stable isotope gas separation device, the chromatographic column unit enables the mixed gas containing the target isotope gas to realize low-temperature adsorption under the cooling effect of the cooling unit, then the temperature is raised through the control unit for desorption, different isotopes are sequentially desorbed through different desorption temperatures of different gases, so that the target isotope gas is collected, the whole device is simple in structure and convenient to operate, and the stable isotope gas separation device is suitable for industrial large-scale production of the stable isotope gas and is an effective stable isotope gas separation device; the application provides a cooling unit is for including the compound cooling unit of different refrigeration methods, supplies cold to the chromatographic column unit through switching different refrigeration methods, can reduce the energy consumption by to a great extent to reduce stable isotope gas's separation cost.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the present application and together with the description, serve to explain the principles of the application. It is obvious that the drawings in the following description are only some embodiments of the application, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
Fig. 1 is a schematic diagram of a column unit in a stable isotope gas separation apparatus of the present application.
List of parts and reference numerals:
201a chromatography column system; 201a primary chromatography column;
201b a secondary chromatography column; 201c a tertiary chromatography column;
202 liquid nitrogen; 203 accommodating means;
a raw material gas flow path; a carrier gas flow path;
thirdly, a waste gas flow path; i, first-stage circulation;
II, secondary circulation; III product flow path.
Detailed Description
The present invention will be described in detail with reference to examples.
Unless otherwise specified, the raw materials in the examples were purchased commercially and used without treatment; the used instruments and equipment adopt the use parameters recommended by manufacturers.
In the embodiment, the collected target isotope gas is characterized by a GC-2018 (Shimadzu) gas chromatograph;
in the examples, the collected target isotope gas was characterized by a TSQ Vantage LC-MS/MS (seemer fly) mass spectrometer.
The gas chromatography has the advantages of low energy consumption, high efficiency, simple operation and the like, and becomes a stable isotope separation technology in gas molecules with great application potential. In the related art, gas chromatography is mainly applied to separation of hydrogen isotopes, and the separation coefficient of stable isotopes (such as carbon, boron and nitrogen isotopes) in other gas molecules is low, so that the application scene of the gas chromatography on the stable isotopes is limited.
Based on this, the application provides a stable isotope gas separation device, can be applied to the separation of stable isotope gas.
The stable isotope gas separation device comprises a chromatographic column unit, a cooling unit, a temperature measurement component and a control unit;
the temperature measuring component is used for measuring the temperature of the chromatographic column unit;
the cooling unit is used for cooling the chromatographic column unit;
the control unit is respectively electrically connected with the temperature measuring component and the cooling unit and is used for controlling the temperature of the chromatographic column unit according to the temperature measured by the temperature measuring component;
the control unit supplies cold to the chromatographic column unit by switching the composite cold supply unit to different refrigeration modes.
Optionally, the cooling unit is a composite cooling unit comprising a liquid nitrogen refrigerator for cooling and a mechanical refrigerator for cooling;
specifically, when the adsorption temperature of the device in the adsorption process is greater than or equal to a preset temperature, a mechanical refrigerator is adopted for cooling, and when the adsorption temperature of the device in the adsorption process is less than the preset temperature, a liquid nitrogen refrigerator is adopted for cooling, so that liquid nitrogen can be saved to a great extent, and the separation cost of stable isotope gas can be reduced, wherein the preset temperature is-50 ℃ to-30 ℃, and preferably the preset temperature is-50 ℃.
In some possible embodiments, when the stable isotope gas separation process is carried out, if the adsorption temperature is greater than or equal to-50 ℃, the mode of cooling by a mechanical refrigerator is switched; if the adsorption temperature is less than-50 ℃, switching to a liquid nitrogen refrigerator cooling mode.
If the current adsorption temperature is reduced to-50 ℃ by a liquid nitrogen refrigerator for cooling, the mode is switched back to a mechanical refrigerator for cooling. Based on the method, liquid nitrogen can be saved to a great extent, and the separation cost of the stable isotope gas is reduced.
Optionally, the apparatus further comprises:
the gas distribution and purification unit is positioned at the gas inlet end of the chromatographic column unit and is used for providing raw gas in the mixed gas for the chromatographic column unit;
a carrier gas supply unit, which is positioned at the gas inlet end of the chromatographic column unit and is used for providing a carrier in the mixed gas and driving the gas in the chromatographic column unit to flow;
optionally, the control unit is electrically connected to the gas distribution and purification unit and the carrier gas supply unit, respectively.
Optionally, the apparatus of the present application further comprises:
a pressure measuring component for measuring the gas pressure within the device;
in particular, since the gas flow paths within the overall device are intercommunicated, the pressure measurement component measures the pressure within the overall device, and in some possible embodiments, the pressure measurement component may be located at the inlet end of the device; in some possible embodiments, the pressure measurement component may also be located at the air outlet end of the device, and of course, the pressure measurement component may also be located at any position of the airflow path in the device according to the actual working requirement, and the application includes but is not limited to the above-mentioned position of pressure measurement.
Alternatively, the pressure measuring part may be at least one of a pressure sensor, a pressure gauge, and the like that can measure pressure.
Optionally, the apparatus of the present application further comprises a mass flow meter, located in the carrier gas supply unit, for measuring the flow of the carrier gas in the carrier gas supply unit.
Optionally, the device of the present application further comprises a gas flow path and a liquid flow path;
the gas flow path comprises gas connecting pipelines of all units in the device, and the liquid flow path is used for circulating flow and collection of liquid in the device;
optionally, the gas flow path and the liquid flow path each comprise a mass flow meter, a pressure measurement component, and a vacuum component.
Optionally, still include valve, joint etc. in air current flow path and the liquid flow path, except adopting the welding mode to connect because of sealed demand, all the other cutting ferrule connected modes of all adopting convenient to detach and maintenance, of course, also can select other connected modes according to actual work demand, this application does not do special requirement to the connected mode of each part.
Preferably, the air flow path of the present application has a low leakage rateAt 10-8Pa m3/s-1。
Optionally, the control unit of the present application employs a high performance data acquisition board and an instrument level signal adjustment system to achieve measurement and control of inlet pressure, carrier gas flow, temperature of the chromatographic column unit, current information, and the like.
Optionally, the chromatography column unit of the present application comprises one or more cascaded chromatography columns;
wherein, can select one or more cascaded chromatographic columns according to the actual separating gas volume and the separation degree of difficulty, for example one, two-stage cascade (two chromatographic columns), three-stage cascade, four-stage cascade, etc. can be applicable to the separation of various different stable isotope gases, and the flexibility of device use is high, expansibility is big.
Optionally, either column is packed with molecular sieves; the molecular sieve structurally has a plurality of pore passages with uniform pore diameters and holes which are regularly arranged, different molecular sieves separate molecules with different sizes and shapes, and in the embodiment, different molecular sieves can adsorb different isotope gases of the same element.
The type and specification of the molecular sieve can be selected according to actual separation requirements, including but not limited to 3A, 4A or 5A type (for example, MS-5A type), and the like, for example, the molecular sieve can be selected from any one of Na type molecular sieve (4A,13X), Ca type molecular sieve (5A,10X) or modified molecular sieve, and the type of the molecular sieve capable of realizing the corresponding adsorption effect can be selected according to actual conditions, which is not particularly required by the present application.
Alternatively, the column unit is immersed in a containing means containing a coolant selected from any one of liquid nitrogen, liquid ammonia, and the like.
Alternatively, the chromatography column unit may comprise a three-stage cascade of chromatography columns, wherein:
the outer diameter of the first-stage chromatographic column is 0.34-0.4 inch;
the first stage chromatography column has a column outer diameter independently selected from the group consisting of 0.34 inch, 0.35 inch, 0.375 inch, 0.385 inch, and 0.4 inch.
The outer diameter of the second-stage chromatographic column is 0.2-0.3 inch;
the second stage chromatography column has an outer column diameter independently selected from the group consisting of 0.2 inch, 0.22 inch, 0.25 inch, 0.28 inch, and 0.3 inch.
The column outer diameter of the third-stage chromatographic column is 0.1-0.15 inch;
the third stage chromatography column has a column outer diameter independently selected from the group consisting of 0.1 inch, 0.11 inch, 0.125 inch, 0.13 inch, and 0.15 inch.
Optionally, the packing density of the molecular sieve in any chromatographic column is 0.5-0.7 g/mL;
the packing density of the molecular sieve in any chromatographic column is independently selected from 0.5g/mL, 0.55g/mL, 0.6g/mL, 0.65g/mL, 0.7 g/mL.
It should be noted that, when the chromatography column unit includes a plurality of cascaded chromatography columns, the size relationship of the column outer diameters of the chromatography columns is not particularly limited, for example, at the air inlet end, the column outer diameters of the plurality of chromatography columns may be sequentially decreased, or sequentially increased, or the size interval may be arranged according to actual requirements; in each separation process, the chromatographic column unit can be used for carrying out multiple cyclic adsorption and desorption processes so as to realize better separation effect.
Optionally, the apparatus of the present application may further comprise an analytical measurement unit, including a chromatograph, a mass spectrometer, etc., for detection analysis of the finally separated stable isotope gas.
The utility model provides a stable isotope gas separation device, chromatographic column unit make the mixed gas who contains target isotope gas adsorb on adsorbing material at low temperature under the cooling effect of cooling unit, later heaies up the desorption through the control unit, and desorption temperature through different gases is different for the isotope gas of in-process difference that heaies up at control chromatographic column unit desorbs in proper order, collects target isotope gas afterwards. The whole device has simple structure and simple and convenient operation, is suitable for industrial large-scale production of stable isotope gas, and is a device for effectively separating stable isotope gas; the utility model provides a cooling unit is for including the compound cooling unit of different refrigeration methods, through switching different refrigeration methods to the chromatographic column unit cooling, can reduce the energy consumption by to a great extent to reduce the gaseous separation cost of stable isotope.
According to an aspect of the present application, a stable isotope gas separation method is provided, which is illustrated below with reference to the following examples:
fig. 1 is a schematic structural diagram of a column unit in a stable isotope gas separation apparatus adopted in this embodiment, and as shown in fig. 1, the column unit 201 includes three columns 201a, 201b, and 201c connected in series, and each column is immersed in a container 203 filled with liquid nitrogen 202. Wherein, the sizes of the chromatographic columns 201a, 201b and 201c are respectively 0.35 inch, 0.25 inch and 0.125 inch, the chromatographic columns are seamlessly welded by adopting imported red copper and are in a double helix shape, the chromatographic columns are filled with spherical MS5A analysis sieves with uniform granularity, and the packing density is 0.6 g/mL. The first-stage circulation I means that the raw material gas can be circularly absorbed and desorbed between the first-stage chromatographic column 201a and the second-stage chromatographic column 201b for many times according to actual working requirements; the secondary circulation II means that the raw material can be circulated between the secondary chromatographic column 201b and the tertiary chromatographic column 201c for multiple times of adsorption and desorption according to actual working requirements.
Example 1
Stable isotope gas10B2H6Separation of
(1) Containing stable isotopes10B2H6Preparing raw material gas, preparing gas in a gas distribution and purification unit, wherein 50 wt% of the raw material gas is taken10B2H6And 50 wt% of11B2H6；
(2) Heating the chromatographic column unit to 250 ℃, introducing high-purity helium gas into the chromatographic column unit through a carrier gas supply unit to activate the chromatographic column unit, and then soaking the chromatographic column unit in a containing device 203 filled with liquid nitrogen;
(3) will contain through the distribution and purification system10B2H6The raw material gas is introduced into a chromatographic column unit, and the chromatographic column unit is cooled by a cooling unit in the process so as to ensure that the temperature of a chromatographic column system reaches-120 ℃; meanwhile, a carrier gas is introduced into the chromatographic column unit through the carrier supply unit to drive the mixed gas to flow from the chromatographic column 201a to the chromatographic columns 201b and 201c in sequence;
(4) controlling the temperature rise rate of the chromatographic column unit to be 5 ℃/min through a control unit to heat the chromatographic column unit to enable the isotope gas in the raw material gas to be desorbed from the surface of the molecular sieve in sequence, wherein the temperature is 500 ℃,10B2H6and (4) desorbing.
(5) Repeating the above steps 4 times (each time for 6 hr), and removing the desorbed target isotope gas by gas chromatograph10B2H6Recording the function relationship between the abundance of the adsorbate and time, and comparing the obtained result with mass spectrum monitoring data, wherein the specific parameters are shown in table 1;
it should be noted that after each sampling, adsorbing and desorbing process, the gas distribution and carrier gas unit needs to be vacuumized to reactivate the chromatographic column; in addition, the raw material gases adopted in the embodiment are all prepared in a laboratory, the abundance of the stable isotope is fixed, and the calculation formula of the product abundance is as follows:
the abundance of the product is equal to the mass of stable isotope gas in the product/mass of raw material gas multiplied by 100%
Examples 2-5 stable isotope gases13CO、15NO、13CH4、15NH3Separation of
Examples 2-5 the parameters and separation procedure were the same as in example 1 except that the feed gas and the adsorption/desorption temperature were different from those in example 1, and the specific parameters are shown in tables 1 and 2.
The compositions of the raw material gases and the corresponding desorption temperatures in examples 2 to 5 are shown in table 1, and the adsorption and desorption parameters are shown in table 2.
TABLE 1
TABLE 2
Therefore, the stable isotope gas separation method based on the stable isotope gas separation device can be suitable for separation of stable isotope gas, has high flexibility and expansibility, and can obtain stable isotope gas with high abundance (up to 98 percent)10B、13C、15The stable isotope gas of any one of N has wide application prospect in the large-scale production of stable isotope products; in addition, in the separation process, carrier gas can be recycled, a coolant can be recycled among the containing devices, the molecular sieve can be reused after being activated, the service life is long, and the method is suitable for industrial large-scale production of products containing stable isotope gas.
Although the present application has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application.
Claims (10)
1. A stable isotope gas separation method, comprising:
a) contacting the mixed gas containing the raw material gas with an adsorbing material for adsorption;
wherein the raw material gas contains target isotope gas;
b) heating to obtain desorption gas;
wherein the desorption gas contains the target isotope gas;
the target isotope gas is a stable isotope gas.
2. The stable isotope gas separation method in accordance with claim 1, wherein the adsorbent material is a molecular sieve.
3. The stable isotope gas separation method in accordance with claim 1, wherein the stable isotope gas contains a stable isotope selected from the group consisting of10B、13C、15And N.
4. The stable isotope gas separation method in accordance with claim 3, wherein the stable isotope is10B, the stable isotope gas is10B2H6(ii) a Alternatively, the first and second electrodes may be,
the stable isotope is13C, the stable isotope gas is selected from13CO、13CO2、13CH4Any one of (a); alternatively, the first and second electrodes may be,
the stable isotope is15N, the stable isotope gas is selected from15NO、15NH3Any one of the above.
5. The stable isotope gas separation method of claim 3, wherein the stable isotope gas is10B2H6The adsorption temperature is-40 to-140 ℃; alternatively, the first and second electrodes may be,
the stable isotope gas is13CO, the adsorption temperature is-150 to-200 ℃; alternatively, the first and second electrodes may be,
the stable isotope gas is13CO2The adsorption temperature is-30 to-130 ℃; alternatively, the first and second electrodes may be,
the stable isotope gas is13CH4The adsorption temperature is-110 to-200 ℃; alternatively, the first and second electrodes may be,
the stable isotope gas is15NO, the adsorption temperature is-100 to-200 ℃; alternatively, the first and second electrodes may be,
the stable isotope gas is15NH3The adsorption temperature is-20-80℃。
6. The stable isotope gas separation method in accordance with claim 1, wherein the rate of temperature rise is 2 to 10 ℃/min.
7. The stable isotope gas separation method of claim 1, wherein the desorption conditions are: the desorption temperature is 500-600 ℃;
preferably, the stable isotope gas is10B2H6The desorption temperature is 500-600 ℃; alternatively, the first and second electrodes may be,
the stable isotope gas is13CO desorption temperature is 500-580 ℃; alternatively, the first and second electrodes may be,
the stable isotope gas is13CO2The desorption temperature is 550-600 ℃; alternatively, the first and second electrodes may be,
the stable isotope gas is13CH4The desorption temperature is 500-600 ℃; alternatively, the first and second electrodes may be,
the stable isotope gas is15The desorption temperature of NO is 500-550 ℃; alternatively, the first and second electrodes may be,
the stable isotope gas is15NH3The desorption temperature is 500-550 ℃.
8. The stable isotope gas separation method in accordance with claim 1, wherein the raw material gas further contains a non-target isotope gas;
the non-target isotope gas contains a non-target isotope;
the non-target isotope and the target isotope are different isotopes of the same element;
the mixed gas also contains carrier gas;
the carrier gas is selected from any one of inert gases;
the flow of the carrier gas is 0.2-1L/min;
the inlet pressure of the raw material gas is 0.1-0.3 Mpa.
9. The stable isotope gas separation method according to any one of claims 1 to 8, wherein if the adsorption temperature is less than a preset temperature, a liquid nitrogen refrigerator is used for cooling;
if the adsorption temperature is greater than or equal to the preset temperature, a mechanical refrigerator is adopted for cooling;
preferably, the preset temperature is-50 to-20 ℃.
10. A stable isotope gas separation apparatus, characterized in that the apparatus comprises a chromatographic column unit, a cooling unit, a temperature measuring part and a control unit;
the temperature measuring component is used for measuring the temperature of the chromatographic column unit;
the cooling unit is used for cooling the chromatographic column unit;
the control unit is respectively electrically connected with the temperature measuring component and the cooling unit and is used for controlling the temperature of the chromatographic column unit according to the temperature measured by the temperature measuring component;
the control unit supplies cold to the chromatographic column unit by switching the composite cold supply unit to different refrigeration modes.
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