A process for the preparation of 13 Apparatus and method for CO standards

Abstract

This application provides a preparation method 13 The apparatus and method for producing CO standards belong to the field of isotope standard manufacturing. The apparatus relies on a multi-stage series distillation unit and adds... 13 CO standard gas distillation column, 12 A CO standard gas distillation column and a standard gas mixing unit with closed-loop control. Electronic specialty gas grades are collected from the end of the multi-stage distillation unit. 13 CO and enrichment from the first-end sample 12 CO was purified to an abundance of over 99.99% through a secondary distillation process to obtain high-abundance CO. 13 CO standard gas and 12 CO standard gas is used, and then dynamically mixed to obtain arbitrary target abundance. 13 CO standard. This application realizes electronic specialty gas grade in a single device. 13 CO and 13 Co-production of CO standard compounds solved 13 While CO standard preparation suffers from high costs and long cycles, it also boasts advantages such as high process integration, precise and controllable product abundance, and high raw material utilization.

Description

Technical Field

[0001] This application relates to the field of isotope standard manufacturing, and more specifically, to a method for preparing... 13 Apparatus and method for CO standard. Background Technology

[0002] In existing technologies, different abundances 13 CO standard (from) 13 CO standard gas and 12 CO standard gas as needed 13 (The CO abundance standard mixture) can provide researchers with a stable reference for accurately calibrating equipment, validating experimental protocols, and exploring isotope effects in fields such as instrument calibration and method validation, medical diagnostics and life sciences, environmental and earth science research, and food traceability and authenticity verification, thereby ensuring the reliability of experimental results and the accuracy of scientific research. Among these applications, the most common is for calibrating the sensitivity and resolution of mass spectrometers, using a mixture of known abundances of CO. 13 CO standards can be used to calibrate the ion source, ion optical system, and detector of a mass spectrometer, ensuring the accuracy of measurement results. Accurate analysis can ensure the stability and reliability of the corresponding production processes.

[0003] However, at present, carbon isotope separation is quite difficult and requires the use of highly demanding CO cryogenic distillation methods. The most common application of CO cryogenic distillation is the preparation of electronic specialty gases. 13 CO (abundance above 99%, purity 99.999%), but to obtain 13 For CO standards, it is necessary to first prepare standards with an abundance of 99.99% or higher. 13 CO standard gas and 12 CO standard gas is then used, and the two are mixed in the required proportions. This typically means requiring two separate, high-cost cryogenic distillation systems (one for producing high abundance CO2). 13 CO, another set of production high abundance 12 (CO), or rely on expensive, unpredictable imported standard gases for dilution. Currently available... 13 The CO2 standard formulation model suffers from significant drawbacks, including high equipment investment, long production cycles, inflexible abundance customization, and low domestic production rates. Consequently, few domestic companies are currently capable of producing it economically, efficiently, and flexibly. 13 Manufacturer of CO standard. Summary of the Invention

[0004] The purpose of this application is to provide a preparation method 13 An apparatus and method for CO standards, the apparatus realizing electronic special gas level 13 CO and 13 The co-production of CO standard compounds effectively solved the problem13 CO standard preparation is characterized by high cost, long cycle and difficulty in domestic production. At the same time, it has the advantages of high process integration, accurate and controllable product abundance and high raw material utilization.

[0005] The embodiments of this application are implemented as follows: In a first aspect, embodiments of this application provide a preparation 13 The apparatus for CO standards includes a multi-stage series distillation unit. 13 CO standard gas distillation column, 12 CO standard gas distillation column and standard gas mixing unit. In this multi-stage series distillation unit along the material conveying direction, the feed inlet of the first distillation column is connected to a gas source storing CO feed gas, and the bottom outlet of the last distillation column can generate CO with an abundance higher than 99%. 13 CO is used to connect with the product collection bottle; 13 The feed inlet of the CO standard gas distillation column is connected to the bottom outlet of the terminal distillation column. 13 The bottom outlet of a CO standard gas distillation column can produce gas with an abundance higher than 99.99%. 13 CO standard gas; 12 The feed inlet of the CO standard gas distillation column is connected to the top outlet of the first distillation column. 12 The top outlet of a CO standard gas distillation column can produce gas with an abundance higher than 99.99%. 12 CO standard gas; the standard gas mixing unit is respectively with... 13 The bottom outlet of the CO standard gas distillation column and 12 The top outlet of the CO standard gas distillation column is connected, and the standard gas mixing unit is configured to be able to... 13 CO standard gas and 12 CO standard gas mixture forms 13 CO standard.

[0006] In the above technical solution, the preparation 13 The CO standard device relies on existing equipment for preparing electronic specialty gases. 13 The construction of a multi-stage CO distillation unit specifically involves the generation of an electronic specialty gas stage at the bottom outlet of the final distillation column within the multi-stage distillation unit. 13 CO and collect most of it as products; on this basis, add 13 A CO standard gas distillation column is used, and its inlet is connected to the bottom outlet of the terminal distillation column to distribute a small portion of the generated electronic specialty gas. 13 CO is delivered to 13 Further distillation in the CO standard gas distillation column can produce electronic specialty gas. 13 The abundance of CO was further increased to over 99.99%, which means that... 13 CO standard gas; at the same time, additional 12A CO standard gas distillation column is used, and its inlet is connected to the top outlet of the first distillation column (an electronic specialty gas with an abundance greater than 99% can be generated at the top outlet). 12 CO), to generate electronic special gas. 12 CO is delivered to 12 Further distillation in the CO standard gas distillation column can produce electronic specialty gas. 12 The abundance of CO was further increased to over 99.99%, which means that... 12 CO standard gas; then add a standard gas mixing unit and mix it with CO standard gas respectively. 13 The bottom outlet of the CO standard gas distillation column and 12 The top outlet of the CO standard gas distillation column is connected to the gas to generate the product. 13 CO standard gas and 12 CO standard gas mixture forms 13 CO standard. That is, the apparatus provided in this application relies on existing methods for preparing electronic specialty gases. 13 The construction of a multi-stage CO distillation unit enables the normal preparation of electronic specialty gases. 13 Simultaneous preparation of CO products to meet higher requirements 13 CO standard (i.e., this device achieves electronic special gas level) 13 CO and 13 (co-production of CO standard products), effectively solving the problem of... 13 CO standard preparation is characterized by high cost, long cycle and difficulty in domestic production. At the same time, it has the advantages of high process integration, accurate and controllable product abundance and high raw material utilization.

[0007] In some alternative implementations, the standard gas mixing unit includes 13 CO standard gas cylinders 12 CO standard gas cylinders 13 CO standard gas flow controller 12 CO standard gas flow controller, gas mixer and standard collection bottle; 13 The inlet of the CO standard gas cylinder and 13 The bottom outlet of the CO standard gas distillation column is connected. 13 The outlet of the CO standard gas cylinder is connected to the mixing chamber inside the gas mixer. 13 CO standard gas flow controller is located at 13 Between the CO standard gas cylinder and the gas mixer, used for adjustment 13 CO standard gas flow rate; 12 The inlet of the CO standard gas cylinder and 12 The top outlet of the CO standard gas distillation column is connected. 12 The outlet of the CO standard gas cylinder is connected to the mixing chamber inside the gas mixer. 12 CO standard gas flow controller is located at 12Between the CO standard gas cylinder and the gas mixer, used for adjustment 12 The flow rate of CO standard gas; the outlet of the gas mixer is connected to the standard collection bottle.

[0008] In the above technical solution, the standard gas mixing unit consists of 13 CO standard gas cylinders 12 CO standard gas cylinders 13 CO standard gas flow controller 12 The system consists of a CO standard gas flow controller, a gas mixer, and a standard substance collection bottle. 13 CO standard gas flow controller and 12 CO standard gas flow controllers are used respectively for... 13 Precise control of the preset abundance value of CO standard. 13 CO standard gas and 12 The flow rate of CO standard gas is adjusted so that the actual abundance of the resulting mixture is consistent with... 13 The preset abundance values ​​of CO standards are relatively close; at the same time, the standard gas mixing unit also has the advantages of simple construction and easy operation.

[0009] In some optional embodiments, the standard gas mixing unit further includes a PLC control module located between the gas mixer and the standard collection bottle, and the PLC control module is connected to... 13 CO standard gas flow controller and 12 The CO standard gas flow controller is electrically connected; the PLC control module is configured to detect the gas mixture at the outlet of the gas mixer to obtain the concentration of CO in the gas mixture. 13 The actual abundance of CO and 13 The system compares the preset abundance values ​​of CO standards and can dynamically adjust the levels based on the comparison results. 13 CO standard gas flow controller flow rate and / or 12 The flow rate of the CO standard gas flow controller.

[0010] In the above technical solution, a PLC control module is added to the standard gas mixing unit. Specifically, the PLC control module is located between the gas mixer and the standard substance collection bottle and is connected to... 13 CO standard gas flow controller and 12 The CO standard gas flow controller is electrically connected and can obtain the flow rate of the mixed gas. 13 The actual abundance of CO and 13 The system compares the preset abundance values ​​of CO standards with those of the two standard gases and dynamically adjusts the flow rates of the two flow controllers based on the comparison results. This setting further increases the mixing accuracy of the two standard gases, ensuring that the actual abundance of the resulting mixture is consistent with the actual abundance values ​​of the standard gases. 13 The CO standard has a higher abundance value than the preset abundance value.

[0011] In some alternative implementations, 13 CO standard gas flow controller and / or 12 All CO standard gas flow controllers are flow controllers with mass accumulation function.

[0012] In the above technical solution, a flow controller with mass accumulation function is used. Under the macro-control of the PLC control module, the mass accumulation function of the flow controller can more accurately control the actual amount of the two standard gases, thereby further increasing the mixing accuracy of the two standard gases, so that the actual abundance of the mixed gas is consistent with... 13 The CO standard has a higher abundance value than the preset abundance value.

[0013] In some alternative implementations, the standard gas mixing unit also includes a temperature control module electrically connected to the gas mixer for controlling temperature fluctuations within the mixing chamber to within ±0.1°C.

[0014] In the above technical solution, the standard gas mixing unit is equipped with a constant temperature control module electrically connected to the gas mixer to control the temperature fluctuation within the mixing chamber within ±0.1℃. This ensures that the two standard gases are always mixed within a preset temperature range, mitigating the impact of temperature fluctuations on gas flow rate and density. Consequently, this helps improve the mixing accuracy and uniformity of the two standard gases, resulting in a mixture with a higher actual abundance than the specified standard gas. 13 The CO standard has a higher abundance value than the preset abundance value.

[0015] In some alternative implementations, the inner walls of the material delivery pipes and the inner walls of the mixing chamber in the standard gas mixing unit are inertized.

[0016] In the above technical solution, the interior of the material conveying pipeline and the inner wall of the mixing chamber are both inertized. Inertization reduces gas adsorption on the inner wall, maintains component stability, and also facilitates thorough mixing of the two standard gases, ensuring that the actual abundance of the resulting mixture is consistent with... 13 The CO standard has a higher abundance value than the preset abundance value.

[0017] In some alternative implementations, the standard gas mixing unit further includes a carrier gas source connected to the standard collection bottle; or, the standard gas mixing unit further includes a dilution module located between the gas mixer and the standard collection bottle.

[0018] In the above technical solution, the standard gas mixing unit is equipped with a carrier gas source connected to the standard substance collection bottle, which can simultaneously prepare standard substance products that meet various filling pressures online, thereby improving... 13The CO standard demonstrates compatibility with testing instruments of different specifications; the standard gas mixing unit incorporates a dilution module between the gas mixer and the standard collection bottle, enabling online simultaneous preparation of various concentrations as needed. 13 CO standard also helps to improve 13 Compatibility of CO standards with testing instruments of different specifications.

[0019] Secondly, embodiments of this application provide a preparation method. 13 The method for preparing CO standards uses the apparatus provided in the first aspect embodiment, and includes the following steps: feeding CO feed gas into a multi-stage series distillation unit for multi-stage distillation to generate a CO standard with an abundance higher than 99% at the bottom outlet of the final distillation column. 13 CO, at the top outlet of the first-stage distillation column, generates an abundance higher than 99%. 12 CO; a portion of the generated 13 CO is collected by transporting it to a product collection bottle. 13 CO electronic special gas, to the remaining part 13 CO is delivered to 13 CO standard gas is purified in a distillation column to achieve the desired results. 13 The bottom outlet of the CO standard gas distillation column produces gas with an abundance higher than 99.99%. 13 CO standard gas; The generated abundance is higher than 99% 12 CO is delivered to 12 CO standard gas is purified in a distillation column to achieve the desired results. 12 The top outlet of the CO standard gas distillation column produces a concentration higher than 99.99%. 12 CO standard gas; the generated 13 CO standard gas and generated 12 CO standard gas is fed into the standard gas mixing unit for gas mixing to form 13 CO standard.

[0020] In the above technical solution, by using the apparatus provided in the first aspect embodiment and preparing according to the above process, it is possible to simultaneously prepare using a single set of apparatus. 13 CO electronic special gas and 13 CO standard, its core advantage lies in: this process can achieve 13 The normal preparation of CO electronic specialty gas, and can also be achieved with the help of a small amount of... 13 The preparation of CO electronic specialty gas is currently very difficult to obtain. 13 CO standard; compared to preparing a single set of equipment 13 CO standard gas, prepared using a separate set of equipment. 12 CO standard gas is then used, and the two standard gases prepared separately are mixed to obtain CO standard gas. 13The preparation process provided in this application, using CO standard materials, also has advantages such as simple process, fewer required equipment, less time consumption, and low cost, and can simultaneously prepare materials with high economic benefits. 13 CO electronic special gas.

[0021] In some alternative implementations, the generated 12 CO is delivered to 12 In the rectification process of a CO standard gas distillation column 12 A CO standard gas distillation column must meet at least one of the following conditions: The temperature at the top of column A is 90 K~95 K, and the pressure at the top of column A is 15 Psia~25 Psia.

[0022] B. The feed flow rate is 50 g / h~150 g / h, and the top discharge flow rate is 10 g / h~60 g / h.

[0023] C. The reflux ratio is 500~2000.

[0024] In the above technical solution, 12 In the preparation steps of CO standard gas, respectively, 12 In a CO standard gas distillation column, key process parameters such as top temperature, top pressure, feed flow rate, top discharge flow rate, and reflux ratio are controlled within the aforementioned ranges to ensure that... 12 Trace amounts of CO are present in CO. 13 CO can be separated more efficiently and thoroughly to prepare products with higher abundance. 12 CO.

[0025] In some alternative implementations, the remaining portion 13 CO is delivered to 13 In the rectification process of a CO standard gas distillation column 13 A CO standard gas distillation column must meet at least one of the following conditions: The temperature at the top of column D is 90 K~95 K, and the pressure at the top of column D is 15 Psia~25 Psia.

[0026] The feed flow rate is 10 g / h to 50 g / h, and the bottom discharge flow rate is 5 g / h to 20 g / h.

[0027] The reflux ratio is 800~2500.

[0028] In the above technical solution, 13 In the preparation steps of CO standard gas, respectively, 13 In a CO standard gas distillation column, key process parameters such as top temperature, top pressure, feed flow rate, bottom flow rate, and reflux ratio are controlled within the aforementioned ranges to ensure that... 13 Trace amounts of CO are present in CO.12 CO can be separated more efficiently and thoroughly to prepare products with higher abundance. 13 CO. Attached Figure Description

[0029] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of this application and should not be regarded as a limitation of the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0030] Figure 1 A preparation method provided in the embodiments of this application 13 A schematic diagram of the CO standard device; Figure 2 This is a schematic diagram of the structure of the first standard gas mixing unit provided in the embodiments of this application; Figure 3 This is a schematic diagram of the structure of a second standard gas mixing unit provided in an embodiment of this application.

[0031] Icon: 10 - Preparation 13 Apparatus for CO standard; 100 - Multistage series distillation unit; 110 - First stage distillation column; 120 - Second stage distillation column; 130 - Isotope recombination device; 140 - Third stage distillation column; 200 - Product collection bottle; 300 - 13 CO standard gas distillation column; 400- 12 CO standard gas distillation column; 500-standard gas mixing unit; 510a- 13 CO standard gas cylinder; 510b- 12 CO standard gas cylinder; 520a- 13 CO standard gas flow controller; 520b- 12 CO standard gas flow controller; 530-Gas mixer; 540-Standard collection bottle; 550-PLC control module; 560-Thermostatic control module; 570-Carrier gas source. Detailed Implementation

[0032] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. The components of the embodiments of this application described and shown in the accompanying drawings can generally be arranged and designed in various different configurations.

[0033] Therefore, the following detailed description of the embodiments of this application provided in the accompanying drawings is not intended to limit the scope of the claimed application, but merely to illustrate selected embodiments of the application. All other embodiments obtained by those skilled in the art based on the embodiments of this application without inventive effort are within the scope of protection of this application.

[0034] It should be noted that similar labels and letters in the following figures indicate similar items. Therefore, once an item is defined in one figure, it does not need to be further defined and explained in subsequent figures.

[0035] In the description of this application, it should be noted that the terms "upper," "lower," "inner," and "outer," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings, or the orientation or positional relationship commonly used when the product is in use. They are used only for the convenience of describing this application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation on this application. In addition, the terms "first," "second," and "third," etc., are used only to distinguish descriptions and should not be construed as indicating or implying relative importance.

[0036] In the description of this application, it should also be noted that, unless otherwise expressly specified and limited, the terms "set up," "install," "connect," and "link" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in this application based on the specific circumstances.

[0037] The following describes one preparation method according to an embodiment of this application. 13 The apparatus and method for obtaining CO standards are described in detail.

[0038] See Figure 1 and Figure 2 In a first aspect, embodiments of this application provide a preparation method for... 13 The CO standard apparatus 10 includes a multi-stage series distillation unit 100. 13 CO standard gas distillation column 300 12 A CO standard gas distillation column 400 and a standard gas mixing unit 500 are included. Along the material conveying direction, in the multi-stage series distillation unit 100, the inlet of the first distillation column is connected to a gas source storing CO feed gas, and the bottom outlet of the last distillation column can generate a product with an abundance higher than 99%. 13 CO is used to connect with product collection bottle 200; 13The feed inlet of the CO standard gas distillation column 300 is connected to the bottom outlet of the terminal distillation column. 13 The bottom outlet of a 300-ton CO standard gas distillation column can produce CO with an abundance higher than 99.99%. 13 CO standard gas; 12 The feed inlet of the CO standard gas distillation column 400 is connected to the top outlet of the first distillation column. 12 The top outlet of a 400 CO standard gas distillation column can produce CO with an abundance higher than 99.99%. 12 CO standard gas; the standard gas mixing unit 500 is respectively with... 13 The bottom outlet of the CO standard gas distillation column 300 and 12 The top outlet of the CO standard gas distillation column 400 is connected, and the standard gas mixing unit 500 is configured to be able to... 13 CO standard gas and 12 CO standard gas mixture forms 13 CO standard.

[0039] It should be noted that all isotopes in the CO feedstock gas are of natural abundance; specifically, 12 CO abundance was approximately 98.9%. 13 The CO abundance is approximately 1.1%. After the CO feed gas undergoes stage-by-stage distillation in the multi-stage series distillation unit 100, a CO abundance higher than 99% can be generated at the top outlet of the first-stage distillation column. 12 CO can be produced at the bottom of the terminal distillation column through two outlets, with an abundance exceeding 99%. 13 CO (i.e.) 13 CO electronic special gas).

[0040] In this application, preparation 13 The CO standard device 10 relies on existing equipment for preparing electronic specialty gases. 13 The construction of a multi-stage CO distillation unit specifically involves the generation of an electronic specialty gas stage at the bottom outlet of the final distillation column within the multi-stage distillation unit. 13 CO and collect most of it as products; on this basis, add 13 CO standard gas distillation column 300 and its inlet is connected to the bottom outlet of the terminal distillation column to distribute a small portion of the generated electronic specialty gas. 13 CO is delivered to 13 Further distillation in the CO standard gas distillation column 300 allows for the production of electronic specialty gases. 13 The abundance of CO was further increased to over 99.99%, which means that... 13 CO standard gas; at the same time, additional 12 A CO standard gas distillation column 400 is used, and its inlet is connected to the top outlet of the first distillation column (the top outlet can generate electronic specialty gas with an abundance greater than 99%). 12CO), to generate electronic special gas. 12 CO is delivered to 12 Further distillation in the CO standard gas distillation column 400 allows for the production of electronic specialty gases. 12 The abundance of CO was further increased to over 99.99%, which means that... 12 CO standard gas; then add a standard gas mixing unit 500 and mix it with CO standard gas respectively. 13 The bottom outlet of the CO standard gas distillation column 300 and 12 The top outlet of the CO standard gas distillation column 400 is connected to the gas to produce... 13 CO standard gas and 12 CO standard gas mixture forms 13 CO standard. That is, the apparatus provided in this application relies on existing methods for preparing electronic specialty gases. 13 The construction of a multi-stage CO distillation unit enables the normal preparation of electronic specialty gases. 13 Simultaneous preparation of CO products to meet higher requirements 13 CO standard (i.e., this device achieves electronic special gas level) 13 CO and 13 (co-production of CO standard products), effectively solving the problem of... 13 CO standard preparation is characterized by high cost, long cycle and difficulty in domestic production. At the same time, it has the advantages of high process integration, accurate and controllable product abundance and high raw material utilization.

[0041] It should be noted that, 13 There is no limit to the specific abundance of CO standards; they can be configured adaptively according to actual needs.

[0042] It should be noted that the form of the multi-stage series distillation unit 100 is not limited, and it can be set up according to the conventional form in this field. See reference. Figure 1 For example, a multi-stage series distillation unit 100 includes a first-stage distillation column 110 (i.e., the first-end distillation column), a second-stage distillation column 120, an isotope recombinator 130, and a third-stage distillation column 140 (i.e., the last-end distillation column) connected in sequence.

[0043] It should be noted that, 13 CO standard gas distillation column 300 and 12 The form of the CO standard gas distillation column 400 is not limited. For example, it can be a single-stage distillation column or a multi-stage cascade distillation column as needed.

[0044] It should be noted that the form of the standard gas mixing unit 500 is not limited, as long as it can mix the two standard gases evenly.

[0045] See Figure 2 As an example, the standard gas mixing unit 500 includes 13 CO standard gas cylinder 510a12 CO standard gas cylinder 510b 13 CO standard gas flow controller 520a 12 CO standard gas flow controller 520b, gas mixer 530 and standard collection bottle 540; 13 The inlet of CO standard gas cylinder 510a and 13 The bottom outlet of the CO standard gas distillation column 300 is connected. 13 The outlet of the CO standard gas cylinder 510a is connected to the mixing chamber inside the gas mixer 530. 13 CO standard gas flow controller 520a is located in 13 Between CO standard gas cylinder 510a and gas mixer 530, for adjustment 13 CO standard gas flow rate; 12 The inlet of CO standard gas cylinder 510b and 12 The top outlet of the CO standard gas distillation column 400 is connected to... 12 The outlet of the CO standard gas cylinder 510b is connected to the mixing chamber inside the gas mixer 530. 12 CO standard gas flow controller 520b is located in 12 Between CO standard gas cylinder 510b and gas mixer 530, for adjustment 12 The flow rate of CO standard gas; the outlet of gas mixer 530 is connected to standard collection bottle 540.

[0046] In this embodiment, the standard gas mixing unit 500 consists of 13 CO standard gas cylinder 510a 12 CO standard gas cylinder 510b 13 CO standard gas flow controller 520a 12 The system consists of a CO standard gas flow controller 520b, a gas mixer 530, and a standard substance collection bottle 540. 13 CO standard gas flow controller 520a and 12 The CO standard gas flow controller 520b is used to determine the flow rate according to... 13 Precise control of the preset abundance value of CO standard. 13 CO standard gas and 12 The flow rate of CO standard gas is adjusted so that the actual abundance of the resulting mixture is consistent with... 13 The preset abundance values ​​of CO standards are relatively close; at the same time, the standard gas mixing unit 500 also has the advantages of simple structure and easy operation.

[0047] See Figure 2 As an example, the standard gas mixing unit 500 also includes a PLC control module 550, which is located between the gas mixer 530 and the standard collection bottle 540. The PLC control module 550 is connected to... 13CO standard gas flow controller 520a and 12 The CO standard gas flow controller 520b is electrically connected; the PLC control module 550 is configured to detect the gas mixture at the outlet of the gas mixer 530 to obtain the concentration of CO in the gas mixture. 13 The actual abundance of CO and 13 The system compares the preset abundance values ​​of CO standards and can dynamically adjust the levels based on the comparison results. 13 The flow rate of CO standard gas flow controller 520a and / or the flow rate of CO standard gas flow controller 520a 12 The flow rate of CO standard gas flow controller 520b.

[0048] In this embodiment, the standard gas mixing unit 500 is additionally equipped with a PLC control module 550. Specifically, the PLC control module 550 is located between the gas mixer 530 and the standard substance collection bottle 540 and is respectively connected to... 13 CO standard gas flow controller 520a and 12 The CO standard gas flow controller 520b is electrically connected and can obtain the flow rate of the mixed gas. 13 The actual abundance of CO and 13 The system compares the preset abundance values ​​of CO standards with those of the two standard gases and dynamically adjusts the flow rates of the two flow controllers based on the comparison results. This setting further increases the mixing accuracy of the two standard gases, ensuring that the actual abundance of the resulting mixture is consistent with the actual abundance values ​​of the standard gases. 13 The CO standard has a higher abundance value than the preset abundance value.

[0049] It should be noted that the specific form of the PLC control module 550 is not limited, as long as it has the above functions. It can be set up in accordance with the conventional form in this field.

[0050] See Figure 2 As an example, 13 CO standard gas flow controller 520a or / and 12 The CO standard gas flow controller 520b is a flow controller with mass accumulation function.

[0051] In this embodiment, a flow controller with mass accumulation function is used. Under the macroscopic control of the PLC control module 550, the mass accumulation function of the flow controller can more accurately control the actual amount of the two standard gases, thereby further increasing the mixing accuracy of the two standard gases, so that the actual abundance of the mixed gas is consistent with... 13 The CO standard has a higher abundance value than the preset abundance value.

[0052] It should be noted that the specific form of the flow controller is not limited, as long as it has the above functions. It can be set up in accordance with the conventional form in this field.

[0053] See Figure 3As an example, the standard gas mixing unit 500 also includes a temperature control module 560, which is electrically connected to the gas mixer 530 and is used to control the temperature fluctuation in the mixing chamber within ±0.1℃.

[0054] In this embodiment, the standard gas mixing unit 500 is equipped with a constant temperature control module 560 electrically connected to the gas mixer 530 to control the temperature fluctuation within the mixing chamber within ±0.1℃. This ensures that the two standard gases are always mixed within a preset temperature range, mitigating the impact of temperature fluctuations on gas flow rate and density. Consequently, this helps improve the mixing accuracy and uniformity of the two standard gases, resulting in a mixture with a higher actual abundance than the specified standard gas. 13 The CO standard has a higher abundance value than the preset abundance value.

[0055] It should be noted that the specific form of the temperature control module 560 is not limited, as long as it has the above-mentioned functions, and it can be set up in accordance with the conventional form in this field.

[0056] As an example, the inner walls of the material conveying pipes and the inner walls of the mixing chamber in the standard gas mixing unit are inertized.

[0057] In this embodiment, the inner walls of the material conveying pipeline and the mixing chamber are both inertized. Inertization reduces gas adsorption on the inner walls, maintains component stability, and also facilitates thorough mixing of the two standard gases, ensuring that the actual abundance of the resulting mixture is consistent with... 13 The CO standard has a higher abundance value than the preset abundance value.

[0058] It should be noted that the specific method of inertization is not limited and can be carried out in accordance with conventional processes in this field.

[0059] As an example, the inertization process includes: first, degreasing the inner wall, then electropolishing the inner wall until Ra ≤ 0.1 μm, and then passivating the inner wall surface with a silanizing agent (e.g., dichlorodimethylsilane) to form a hydrophobic, inert siloxane layer.

[0060] In this embodiment, the aforementioned inertization treatment can effectively suppress the adsorption-desorption equilibrium fluctuations between CO molecules and the inner metal wall, effectively improving the product abundance drift problem caused by the tube wall adsorption effect. This helps to prepare a mixture with smaller abundance deviation (i.e., the actual mixed gas abundance is closer to the preset mixed gas abundance value). 13 CO standard.

[0061] See Figure 3As an example, the standard gas mixing unit 500 also includes a carrier gas source 570, which is connected to the standard collection bottle 540; or, the standard gas mixing unit 500 also includes a dilution module (not shown in the figure), which is located between the gas mixer 530 and the standard collection bottle 540.

[0062] In this embodiment, the standard gas mixing unit 500 is equipped with a carrier gas source connected to the standard substance collection bottle 540, which can simultaneously prepare standard substance products that meet various filling pressures online, thereby improving... 13 The CO standard demonstrates compatibility with testing instruments of different specifications; the standard gas mixing unit 500 incorporates a dilution module between the gas mixer 530 and the standard collection bottle 540, enabling the online synchronous preparation of various concentrations as needed. 13 CO standard also helps to improve 13 Compatibility of CO standards with testing instruments of different specifications.

[0063] It should be noted that, regarding the preparation 12 Unless otherwise specified or limited, the functional devices or structural units in the CO standard device can be set up in accordance with the conventional form in this field.

[0064] Secondly, embodiments of this application provide a preparation method. 13 The method for preparing CO standards uses the apparatus provided in the first aspect embodiment, and includes the following steps: feeding CO feed gas into a multi-stage series distillation unit for multi-stage distillation to generate a CO standard with an abundance higher than 99% at the bottom outlet of the final distillation column. 13 CO, at the top outlet of the first-stage distillation column, generates an abundance higher than 99%. 12 CO; a portion of the generated 13 CO is collected by transporting it to a product collection bottle. 13 CO electronic special gas, to the remaining part 13 CO is delivered to 13 CO standard gas is purified in a distillation column to achieve the desired results. 13 The bottom outlet of the CO standard gas distillation column produces gas with an abundance higher than 99.99%. 13 CO standard gas; The generated abundance is higher than 99% 12 CO is delivered to 12 CO standard gas is purified in a distillation column to achieve the desired results. 12 The top outlet of the CO standard gas distillation column produces a concentration higher than 99.99%. 12 CO standard gas; the generated 13 CO standard gas and generated 12 CO standard gas is fed into the standard gas mixing unit for gas mixing to form 13 CO standard.

[0065] In this application, by using the apparatus provided in the first aspect embodiment and following the above-described process, it is possible to simultaneously prepare [the product] using a single set of apparatus. 13 CO electronic special gas and 13 CO standard, its core advantage lies in: this process can achieve 13 The normal preparation of CO electronic specialty gas, and can also be achieved with the help of a small amount of... 13 The preparation of CO electronic specialty gas is currently very difficult to obtain. 13 CO standard; compared to preparing a single set of equipment 13 CO standard gas, prepared using a separate set of equipment. 12 CO standard gas is then used, and the two standard gases prepared separately are mixed to obtain CO standard gas. 13 The preparation process provided in this application, using CO standard materials, also has advantages such as simple process, fewer required equipment, less time consumption, and low cost, and can simultaneously prepare materials with high economic benefits. 13 CO electronic special gas.

[0066] It should be noted that an abundance higher than 99% was obtained by using a multi-stage series distillation unit. 13 CO and abundance above 99% 12 The specific process of CO can be carried out in accordance with conventional processes in the field, and no specific limitations are made in the embodiments of this application.

[0067] As an example, the generated 12 CO is delivered to 12 In the rectification process of a CO standard gas distillation column 12 A CO standard gas distillation column must meet at least one of the following conditions: A. The top temperature of the column is 90 K to 95 K (e.g., but not limited to any one of 90 K, 91 K, 92 K, 93 K, 94 K and 95 K or any range between two), and the top pressure of the column is 15 Psia to 25 Psia (e.g., but not limited to any one of 15 Psia, 18 Psia, 20 Psia, 22 Psia and 25 Psia or any range between two).

[0068] B. The feed flow rate is 50 g / h to 150 g / h (e.g., but not limited to any one of 50 g / h, 80 g / h, 100 g / h, 120 g / h and 150 g / h or any range between two), and the top discharge flow rate is 10 g / h to 60 g / h (e.g., but not limited to any one of 10 g / h, 20 g / h, 30 g / h, 40 g / h, 50 g / h and 60 g / h or any range between two).

[0069] C. The reflux ratio is 500 to 2000 (e.g., but not limited to any one of the reflux ratios of 500, 800, 1000, 1500 and 2000, or any range between two).

[0070] In this embodiment, 12 In the preparation steps of CO standard gas, respectively, 12 In a CO standard gas distillation column, key process parameters such as top temperature, top pressure, feed flow rate, top discharge flow rate, and reflux ratio are controlled within the aforementioned ranges to ensure that... 12 Trace amounts of CO are present in CO. 13 CO can be separated more efficiently and thoroughly to prepare products with higher abundance. 12 CO.

[0071] As an example, 12 The CO standard gas distillation column has an inner diameter of 50 mm to 150 mm (e.g., but not limited to any one of 50 mm, 80 mm, 100 mm, 120 mm and 150 mm or any range between two), and the packing is selected from at least one of triangular spiral packing, Cannon packing, calendered ring packing and Dixon packing with an average particle size of 1 mm to 10 mm (e.g., but not limited to average particle sizes of 1 mm, 2 mm, 4 mm, 6 mm, 8 mm and 10 mm).

[0072] As an example, the remaining part 13 CO is delivered to 13 In the rectification process of a CO standard gas distillation column 13 A CO standard gas distillation column must meet at least one of the following conditions: The temperature at the top of column D is 90 K to 95 K (e.g., but not limited to any one of 90 K, 91 K, 92 K, 93 K, 94 K and 95 K or any range between two), and the pressure at the top of column D is 15 Psia to 25 Psia (e.g., but not limited to any one of 15 Psia, 18 Psia, 20 Psia, 22 Psia and 25 Psia or any range between two).

[0073] E The feed flow rate is 10 g / h to 50 g / h (e.g., but not limited to any one of 10 g / h, 20 g / h, 30 g / h, 40 g / h and 50 g / h or any range between two), and the bottom discharge flow rate is 5 g / h to 20 g / h (e.g., but not limited to any one of 5 g / h, 10 g / h, 15 g / h and 20 g / h or any range between two).

[0074] F reflux ratio is 800~2500 (e.g., but not limited to any point value of 800, 1000, 1500, 2000 and 2500 or any range between two).

[0075] In this embodiment, 13 In the preparation steps of CO standard gas, respectively, 13 In a CO standard gas distillation column, key process parameters such as top temperature, top pressure, feed flow rate, bottom flow rate, and reflux ratio are controlled within the aforementioned ranges to ensure that... 13 Trace amounts of CO are present in CO. 12 CO can be separated more efficiently and thoroughly to prepare products with higher abundance. 13 CO.

[0076] As an example, 13 The CO standard gas distillation column has an inner diameter of 50 mm to 150 mm (e.g., but not limited to any one of 50 mm, 80 mm, 100 mm, 120 mm and 150 mm or any range between two), and the packing is selected from at least one of triangular spiral packing, Cannon packing, calendered ring packing and Dixon packing with an average particle size of 1 mm to 10 mm (e.g., but not limited to average particle sizes of 1 mm, 2 mm, 4 mm, 6 mm, 8 mm and 10 mm).

[0077] It should be noted that in the preparation 13 In the process of producing CO standard materials, any processes or steps not specified or limited may be performed in accordance with conventional processes in this field.

[0078] The technical solution of this application will be specifically described below with reference to the embodiments.

[0079] Example 1 This application provides a method for preparing... 13 The method for CO standards includes the following steps: use Figure 1 The device shown converts CO feed gas ( 12 CO abundance was approximately 98.9%.13 A CO concentration of approximately 1.1% is fed into a three-stage series distillation unit for multi-stage distillation, resulting in a CO concentration of 99.2% at the bottom outlet of the final distillation column (i.e., the third stage column). 13 CO, at the top outlet of the first-stage distillation column (i.e., the first-stage distillation column), produces CO with an abundance of 99.5%. 12 CO.

[0080] The generated volume has an abundance of 99.3%. 13 CO is collected by transporting it to a product collection bottle. 13 CO electronic special gas, to the remaining part 13 CO is delivered to 13 CO standard gas is distilled in a distillation column (specifically, 13 The CO standard gas distillation column has an inner diameter of 100 mm, uses stainless steel triangular spiral packing with an average particle size of 2 mm, a top temperature of 92 K, a top pressure of 20 Psia, a feed flow rate of 30 g / h, and a reflux ratio of 1200. 13 The CO standard gas distillation column produced 99.992% CO at the bottom outlet. 13 CO standard gas; the generated abundance is 99.5% 12 CO is delivered to 12 CO standard gas is distilled in a distillation column (specifically, 12 The CO standard gas distillation column has an inner diameter of 80 mm, uses stainless steel triangular spiral packing with an average particle size of 2 mm, a top temperature of 92 K, a top pressure of 20 Psia, a feed flow rate of 100 g / h, and a reflux ratio of 800. 12 The CO standard gas distillation column produced 99.997% CO at the top outlet. 12 CO standard gas.

[0081] The generated abundance is 99.992%. 13 CO standard gas and an abundance of 99.997% 12 CO standard gas is delivered to Figure 2 The standard gas mixing unit shown is used for mixing, wherein, 13 The preset flow rate of CO standard gas and 12 The preset flow rate ratio for CO standard gas is 9:1. 13 CO standard gas flow controller and 12 The real-time flow rate of the CO standard gas flow controller is regulated by the PLC control module and the built-in mass accumulation function of the standard gas flow controller to deliver the mixed gas to the standard collection bottle. Simultaneously, the carrier gas source fills the standard collection bottle to a preset pressure (6 bar), resulting in an abundance of 90.01%. 13CO standard.

[0082] It should be emphasized that, according to preliminary calculations, if two independent cryogenic distillation systems are used to prepare products with an abundance of 99.99% or higher... 13 CO standard gas and 12 CO standard gas was used, and then a static mixing method was employed to prepare a gas with approximate abundance. 13 Compared to the preparation method described in this application, the equipment investment cost of the CO standard is approximately 2.5 times that of the preparation method described in this application, the production cycle is extended by about 60%, and it cannot be achieved... 13 CO electronic special gas and 13 Co-production of CO standard.

[0083] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A method for preparing 13 The device for CO standard is characterized in that... include: A multi-stage series distillation unit, along the material conveying direction, wherein the inlet of the first distillation column is connected to a gas source storing CO feed gas, and the bottom outlet of the last distillation column can generate a product with an abundance higher than 99%. 13 CO is used to connect with the product collection bottle; 13 CO standard gas distillation column, the 13 The inlet of the CO standard gas distillation column is connected to the bottom outlet of the terminal distillation column. 13 The bottom outlet of a CO standard gas distillation column can produce gas with an abundance higher than 99.99%. 13 CO standard gas; 12 CO standard gas distillation column, the 12 The feed inlet of the CO standard gas distillation column is connected to the top outlet of the first-end distillation column. 12 The top outlet of a CO standard gas distillation column can produce gas with an abundance higher than 99.99%. 12 CO standard gas; The standard gas mixing unit is respectively connected to the standard gas mixing unit. 13 The bottom outlet of the CO standard gas distillation column and the aforementioned 12 The top outlet of the CO standard gas distillation column is connected, and the standard gas mixing unit is configured to be able to... 13 CO standard gas and the aforementioned 12 CO standard gas mixture forms 13 CO standard.

2. The preparation according to claim 1 13 The device for CO standard is characterized in that... The standard gas mixing unit includes 13 CO standard gas cylinders 12 CO standard gas cylinders 13 CO standard gas flow controller 12 CO standard gas flow controller, gas mixer and standard collection bottle; The 13 The inlet of the CO standard gas cylinder and the aforementioned 13 The bottom outlet of the CO standard gas distillation column is connected to the... 13 The outlet of the CO standard gas cylinder is connected to the mixing chamber inside the gas mixer. 13 The CO standard gas flow controller is located in the 13 Between the CO standard gas cylinder and the gas mixer, for adjusting the 13 CO standard gas flow rate; The 12 The inlet of the CO standard gas cylinder and the aforementioned 12 The top outlet of the CO standard gas distillation column is connected to the... 12 The outlet of the CO standard gas cylinder is connected to the mixing chamber inside the gas mixer. 12 The CO standard gas flow controller is located in the 12 Between the CO standard gas cylinder and the gas mixer, for adjusting the 12 CO standard gas flow rate; The outlet of the gas mixer is connected to the standard sample collection bottle.

3. The preparation according to claim 2 13 The device for CO standard is characterized in that... The standard gas mixing unit further includes a PLC control module, which is located between the gas mixer and the standard substance collection bottle. The PLC control module is connected to the gas mixer and the standard substance collection bottle respectively. 13 CO standard gas flow controller and the 12 Electrical connection of CO standard gas flow controller; The PLC control module is configured to detect the gas mixture at the outlet of the gas mixer to obtain the concentration of the gas mixture. 13 The actual abundance of CO and 13 The CO standard is compared with the preset abundance value, and the value can be dynamically adjusted based on the comparison result. 13 The flow rate of the CO standard gas flow controller and / or the aforementioned 12 The flow rate of the CO standard gas flow controller.

4. The preparation according to claim 3 13 The device for CO standard is characterized in that... The 13 CO standard gas flow controller or / and the aforementioned 12 All CO standard gas flow controllers are flow controllers with mass accumulation function.

5. Preparation according to any one of claims 2 to 4 13 The device for CO standard is characterized in that... The standard gas mixing unit also includes a constant temperature control module, which is electrically connected to the gas mixer to ensure that the temperature fluctuation deviation in the mixing chamber does not exceed ±0.1℃.

6. Preparation according to any one of claims 2 to 4 13 The device for CO standard is characterized in that... The inner walls of the material conveying pipes and the inner walls of the mixing chamber in the standard gas mixing unit are both inertized.

7. Preparation according to any one of claims 2 to 4 13 The device for CO standard is characterized in that... The standard gas mixing unit also includes a carrier gas source, which is connected to the standard substance collection bottle; Alternatively, the standard gas mixing unit may further include a dilution module located between the gas mixer and the standard collection bottle.

8. A method for preparing 13 The method for CO standard is characterized by... The preparation is carried out using the apparatus described in any one of claims 1 to 7, and the method includes the following steps: The CO feed gas is fed into the multi-stage series distillation unit for multi-stage distillation, so as to generate a product with an abundance higher than 99% at the bottom outlet of the final distillation column. 13 CO, at the top outlet of the first-stage distillation column, generates an abundance higher than 99%. 12 CO; A portion of the generation 13 CO is collected by conveying it to the product collection bottle. 13 CO electronic special gas, to the remaining part 13 CO is delivered to the 13 The CO standard gas is distilled in a distillation column to achieve the desired result. 13 The bottom outlet of the CO standard gas distillation column produces gas with an abundance higher than 99.99%. 13 CO standard gas; The generated abundance is higher than 99%. 12 CO is delivered to the 12 The CO standard gas is distilled in a distillation column to achieve the desired result. 12 The top outlet of the CO standard gas distillation column produces a concentration higher than 99.99%. 12 CO standard gas; The generated 13 CO standard gas and the generated 12 CO standard gas is fed into the standard gas mixing unit for gas mixing to form 13 CO standard.

9. The preparation according to claim 8 13 The method for CO standard is characterized by... The generated 12 CO is delivered to the 12 In the step of distillation in a CO standard gas distillation column, the... 12 A CO standard gas distillation column must meet at least one of the following conditions: A. The temperature at the top of the column is 90 K~95 K, and the pressure at the top of the column is 15 Psia~25 Psia; B. The feed flow rate is 50 g / h~150 g / h, and the top discharge flow rate is 10 g / h~60 g / h; C. The reflux ratio is 500~2000.

10. The preparation according to claim 8 or 9 13 The method for CO standard is characterized by... The remaining part 13 CO is delivered to the 13 In the step of distillation in a CO standard gas distillation column, the... 13 A CO standard gas distillation column must meet at least one of the following conditions: The temperature at the top of column D is 90 K~95 K, and the pressure at the top of column D is 15 Psia~25 Psia; E The feed flow rate is 10 g / h~50 g / h, and the bottom discharge flow rate is 5 g / h~20 g / h; The reflux ratio is 800~2500.

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