Patent Application
20240239665
This application claims priority to Chinese Patent Application No. 202311640673.9 filed Dec. 1, 2023, the disclosure of which is incorporated herein by reference in its entirety.
The present application belongs to the technical field of carbon dioxide preparation, and specifically relates to a system for preparing isotope-labeled carbon dioxide and a method therefor.
Under the background of “carbon peak and carbon neutrality”, the related scientific researches on the capture, conversion, and utilization of carbon dioxide have become recognized research hotspots. During the conversion reaction of carbon dioxide, the isotope tracking experiment is an important method to study the conversion pathway and reaction mechanism of CO2, and carbon dioxide labeled with oxygen isotope is the main material for the isotope experiment. However, the carbon dioxide labeled with oxygen isotope has a high price due to its complex preparation, separation, and purification processes, which limits the application of the carbon dioxide labeled with oxygen isotope in related research fields.
CN114436260A discloses a device and a method for preparing carbon monoxide and carbon dioxide labeled with oxygen isotope. Oxalic acid labeled with oxygen isotope is decomposed by heating in a reactor to obtain CO2, CO, and H2O labeled with oxygen isotope, and then the CO2, CO, and H2O labeled with oxygen isotope are collected separately at different temperatures through a collection bottle and a freezing device. In this method, the preparation process, separation, and purification of the product are simple and efficient, the utilization rate of the oxygen isotope is high, and the carbon dioxide product with an 0-18 abundance of more than 95% can be obtained. However, in this method, oxalic acid labeled with oxygen isotope used as an isotope source is expensive, the condition of separation and purification is harsh, and the freezing temperature are required to be less than or equal to −100° C.
Therefore, it is of great significance to develop a simple, environmental-friendly, efficient and low-cost system for preparing oxygen-18 labeled carbon dioxide and a method therefor to meet the application needs of related research fields.
An object of the present application is to provide a system for preparing isotope-labeled carbon dioxide and a method therefor, which have widely available and low-cost raw materials, mild preparation conditions, simple process, and good economic benefits and application prospects.
To achieve the above object, the present application adopts the following technical solutions.
In a first aspect, the present application provides a system for preparing isotope-labeled carbon dioxide, and the system comprises: a preparation unit, a raw material storage device for heavy-oxygen water, a raw material storage device for carbon dioxide, a product storage device, and a recovery and storage device for heavy-oxygen water;
The system provided by the present application has a simple structure; by adopting the heavy-oxygen water which has a wide source and low cost as an oxygen isotope source and utilizing the oxygen-exchange reaction, the replacement of oxygen-16 in normal carbon dioxide by oxygen-18 in heavy-oxygen water is achieved to obtain the oxygen-18 labeled carbon dioxide product. The process is simple and pollution-free, the utilization rate of oxygen isotope is high, the conditions of separation and purification are mild, and the system has good economic benefits and application prospects.
Preferably, the system comprises at least one preparation unit.
For the system provided by the present application, the preparation unit can be flexibly set up according to the purity requirements of the product, and the setting of the preparation unit is convenient and satisfies the needs of different products.
Preferably, in a case where the system comprises two or more preparation units, an inlet of the heating vaporization device of a next preparation unit is respectively connected to the raw material storage device for heavy-oxygen water and the gas-phase outlet of the gas-liquid separation device of a previous preparation unit along the flow direction of materials in the system.
Preferably, in a case where the system comprises two or more preparation units, a heat-exchange device is further arranged between two adjacent preparation units;
Preferably, the catalytic material comprises any one or a combination of at least two of γ-Al2O3, CeO2, or anatase titanium dioxide, and typical but non-limiting combinations comprise a combination of γ-Al2O3 and CeO2, a combination of CeO2 and anatase titanium dioxide, a combination of γ-Al2O3 and anatase titanium dioxide, or a combination of γ-Al2O3, CeO2, and anatase titanium dioxide.
In a second aspect, the present application provides a preparation method for isotope-labeled carbon dioxide, and the preparation method adopts the system according to the first aspect.
Preferably, the preparation method comprises the following steps:
(1) vaporizing heavy-oxygen water, and then mixing the heavy-oxygen water with carbon dioxide to obtain a mixed gas;
(2) catalyzing the mixed gas obtained in step (1) with a catalytic material to subject the heavy-oxygen water and the carbon dioxide to an oxygen-exchange reaction, wherein the 16O in the carbon dioxide is replaced by 18O in the heavy-oxygen water to generate isotope-labeled carbon dioxide, and the 18O in the heavy-oxygen water is replaced by 16O; and
(3) liquefying the heavy-oxygen water after the reaction, and subjecting the same and the carbon dioxide after the reaction to gas-liquid separation to obtain the isotope-labeled carbon dioxide.
Preferably, a molar ratio of the heavy-oxygen water to the carbon dioxide in step (1) is (2-5):1, which can be, for example, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, or 5:1; however, the molar ratio is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
Preferably, the vaporization in step (1) is performed at a temperature of 100-300° C., which can be, for example, 100° C., 120° C., 140° C., 150° C., 160° C., 180° C., 200° C., 220° C., 240° C., 250° C., 260° C., 280° C., or 300° C.; however, the temperature is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
Preferably, the oxygen-exchange reaction in step (2) is performed at a volumetric space velocity of 5000-100000 h−1, which can be, for example, 5000 h−1, 10000 h−1, 15000 h−1, 20000 h−1, 30000 h−1, 40000 h−1, 500000 h−1, 60000 h−1, 70000 h−1, 80000 h−1, 90000 h−1, or 100000 h−1; however, the volumetric space velocity is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
Preferably, the liquefaction in step (3) is performed at a temperature of −10° C. to 20° C., which can be, for example, −10° C., −5° C., 0° C., 5° C., 10° C., 15° C., or 20° C.; however, the temperature is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
Compared with the prior art, the present application has the following beneficial effects.
The system provided by the present application has a simple structure; by adopting the heavy-oxygen water which has a wide source and low cost as an oxygen isotope source and utilizing the oxygen-exchange reaction, the replacement of oxygen-16 in normal carbon dioxide by oxygen-18 in heavy-oxygen water is achieved to obtain the oxygen-18 labeled carbon dioxide produce. The process is simple and pollution-free, the utilization rate of oxygen isotope is high, the conditions of separation and purification are mild, and the system has good economic benefits and application prospects.
1—raw material storage device for heavy-oxygen water; 2—raw material storage device for carbon dioxide; 3—primary heating vaporization device; 4—primary oxygen-exchange reaction device; 5—catalytic material; 6—primary gas-liquid separation device; 7—secondary heating vaporization device; 8—secondary oxygen-exchange reaction device; 9 —heat-exchange device; 10—secondary gas-liquid separation device; 11—tertiary heating vaporization device; 12—tertiary oxygen-exchange reaction device; 13—heat-exchange device; 14—tertiary gas-liquid separation device; 15—product storage device; and 16—recovery and storage device for heavy-oxygen water.
The technical solutions of the present application are further illustrated via embodiments. It should be understood by those skilled in the field that the examples are merely used for understanding the present application and should not be regarded as a specific limitation to the present application.
The example provides a system for preparing isotope-labeled carbon dioxide, as shown in
The example provides a system for preparing isotope-labeled carbon dioxide, and the system comprises: a primary preparation unit, a secondary preparation unit, a raw material storage device for heavy-oxygen water 1, a raw material storage device for carbon dioxide 2, a product storage device 15, and a recovery and storage device for heavy-oxygen water 16, and a heat-exchange device 9;
This application example provides a preparation method for isotope-labeled carbon dioxide. In the preparation method, the system provided in Example 1 was used, and the preparation method comprises the following steps:
(1) heavy-oxygen water (H218O in liquid form) provided by a raw material storage device for heavy-oxygen water 1 was passed into a primary heating vaporization device 3, then the heavy-oxygen water was vaporized into a gas phase, carbon dioxide (CO2) was provided by a raw material storage device for carbon dioxide 2, and the gas-phase heavy-oxygen water was mixed with the carbon dioxide, wherein the molar ratio of the heavy-oxygen water and the carbon dioxide was 3:1, and a temperature of the mixed gas at an outlet of the primary heating vaporization device 3 was 120° C.;
(2) the mixed gas of H218O and CO2 were introduced into a primary oxygen-exchange reaction device 4, wherein a reaction temperature of the primary oxygen-exchange reaction device 4 was 110° C., and a volumetric space velocity was 10000 h−1; and under the action of the catalytic material γ-Al2O3, H218O was decomposed, and reacted with CO2 adsorbed on the material for oxygen exchange, where 16O in the CO2 was replaced by 18O in the H218O to generate oxygen-18 labeled carbon dioxide (C18O16O and C18O18O), and 18O in the H218O was replaced by 16O to generate H216O;
(3) the gas after the oxygen-exchange reaction was cooled in a gas-liquid separation device 6 at a cooling temperature of −3° C., and a separated liquid-phase water (H218O and H216O) entered a recovery and storage device for heavy-oxygen water 16, and a separated gas-phase carbon dioxide (C16O16O, C18O16O, and C18O18O) was heated to 80° C. by a heat-exchange device 9; and
(4) the gas-phase carbon dioxide (C16O16O, C18O16O, and C18O18O) after a primary oxygen-exchange reaction and the heavy-oxygen water were sequentially subjected to a secondary preparation unit and a tertiary preparation unit to perform the same vaporization, oxygen-exchange reaction, and gas-liquid separation as steps (1) to (3), and the obtained isotope-labeled carbon dioxide product entered a product storage device 15.
In this application example, a proportion of C18O18O in CO2 at a gas-phase outlet of the primary gas-liquid separation device 6 was 52%, a proportion of C18O18O in CO2 at a gas-phase outlet of the secondary gas-liquid separation device 10 was 84%, and a proportion of C18O18O in CO2 at a gas-phase outlet of the tertiary gas-liquid separation device 14 was 98%.
This application example provides a preparation method for isotope-labeled carbon dioxide. In the preparation method, the system provided in Example 1 was used, and the preparation method comprises the following steps:
(1) heavy-oxygen water (H218O in liquid form) provided by a raw material storage device for heavy-oxygen water 1 was passed into a primary heating vaporization device 3, the heavy-oxygen water was vaporized into a gas phase, carbon dioxide (CO2) was provided by a raw material storage device for carbon dioxide 2, and the gas phase heavy-oxygen water was mixed with the carbon dioxide, wherein the molar ratio of the heavy-oxygen water and the carbon dioxide was 2:1, and a temperature of the mixed gas at an outlet of the primary heating vaporization device 3 was 100° C.;
(2) the mixed gas of H218O and CO2 were introduced into a primary oxygen-exchange reaction device 4, wherein a reaction temperature of the primary oxygen-exchange reaction device 4 was 110° C., and a volumetric space velocity was 5000 h−1; and under the action of the catalytic material γ-Al2O3, H218O was decomposed, and reacted with CO2 adsorbed on the material for oxygen exchange, where 16O in the CO2 was replaced by 18O in the H218O to generate oxygen-18 labeled carbon dioxide (C18O16O and C18O18O), and 18O in the H218O was replaced by 16O to generate H216O;
(3) the gas after the oxygen-exchange reaction was cooled in a gas-liquid separation device 6 at a cooling temperature of −10° C., and a separated liquid phase water (H218O and H216O) entered a recovery and storage device for heavy-oxygen water 16, and a separated gas phase carbon dioxide (C16O16O, C18O16O, and C18O18O) was heated to 80° C. by a heat-exchange device 9; and
(4) the gas phase carbon dioxide (C16O16O, C18O16O, and C18O18O) after a primary oxygen-exchange reaction and the heavy-oxygen water were sequentially subjected to a secondary preparation unit and a tertiary preparation unit to perform the same vaporization, oxygen-exchange reaction, and gas-liquid separation as steps (1) to (3), and the obtained isotope-labeled carbon dioxide product entered a product storage device 15.
In this application example, a proportion of C18O18O in CO2 at a gas-phase outlet of the primary gas-liquid separation device 6 was 45%, a proportion of C18O18O in CO2 at a gas-phase outlet of the secondary gas-liquid separation device 10 was 72%, and a proportion of C18O18O in CO2 at a gas-phase outlet of the tertiary gas-liquid separation device 14 was 88%.
This application example provides a preparation method for isotope-labeled carbon dioxide. In the preparation method, the system provided in Example 1 was used, and the preparation method comprises the following steps:
(1) heavy-oxygen water (H218O in liquid form) provided by a raw material storage device for heavy-oxygen water 1 was passed into a primary heating vaporization device 3, the heavy-oxygen water was vaporized into a gas phase, carbon dioxide (CO2) was provided by a raw material storage device for carbon dioxide 2, and the gas phase heavy-oxygen water was mixed with the carbon dioxide, wherein the molar ratio of the heavy-oxygen water and the carbon dioxide was 5:1, and a temperature of the mixed gas at an outlet of the primary heating vaporization device 3 was 300° C.;
(2) the mixed gas of H218O and CO2 were introduced into a primary oxygen-exchange reaction device 4, wherein a reaction temperature of the primary oxygen-exchange reaction device 4 was 110° C., and a volumetric space velocity was 100000 h−1; and under the action of the catalytic material γ-Al2O3, H218O was decomposed, and reacted with CO2 adsorbed on the material for oxygen exchange, where 16O in the CO2 was replaced by 18O in the H218O to generate oxygen-18 labeled carbon dioxide (C18O16O and C18O18O), and 18O in the H218O was replaced by 16O to generate H216O;
(3) the gas after the oxygen-exchange reaction was cooled in a gas-liquid separation device 6 at a cooling temperature of 20° C., and a separated liquid phase water (H218O and H216O) entered a recovery and storage device for heavy-oxygen water 16, and a separated gas phase carbon dioxide (C16O16O, C18O16O, and C18O18O) was heated to 80° C. by a heat-exchange device 9; and
(4) the gas phase carbon dioxide (C16O16O, C18O16O, and C18O18O) after a primary oxygen-exchange reaction and the heavy-oxygen water were sequentially subjected to a secondary preparation unit and a tertiary preparation unit to perform the same vaporization, oxygen-exchange reaction, and gas-liquid separation as steps (1) to (3), and the obtained isotope-labeled carbon dioxide product entered a product storage device 15.
In this application example, a proportion of C18O18O in CO2 at a gas-phase outlet of the primary gas-liquid separation device 6 was 64%, a proportion of C18O18O in CO2 at a gas-phase outlet of the secondary gas-liquid separation device 10 was 87%, and a proportion of C18O18O in CO2 at a gas-phase outlet of the tertiary gas-liquid separation device 14 was 99%.
This application example provides a preparation method for isotope-labeled carbon dioxide. In the preparation method, the system provided in Example 1 was used. This application example differs from Application Example 1 in that the molar ratio of the heavy-oxygen water to the carbon dioxide in the primary heating vaporization device 3, the secondary heating vaporization device 7, and the tertiary heating vaporization device are 2:1, 3:1, and 4:1, respectively, and the rest are the same as in Application Example 1.
In this application example, a proportion of C18O18O in CO2 at a gas-phase outlet of the primary gas-liquid separation device 6 was 40%, a proportion of C18O18O in CO2 at a gas-phase outlet of the secondary gas-liquid separation device 10 was 75%, and a proportion of C18O18O in CO2 at a gas-phase outlet of the tertiary gas-liquid separation device 14 was 96%.
This application example provides a preparation method for isotope-labeled carbon dioxide. In the preparation method, the system provided in Example 1 was used. This application example differs from Application Example 1 in that the catalytic material in the primary oxygen-exchange reaction device 4, the secondary oxygen-exchange reaction device 8, and the tertiary oxygen-exchange reaction device 12 are replaced by CeO2 with an equal amount.
In this application example, a proportion of C18O18O in CO2 at a gas-phase outlet of the primary gas-liquid separation device 6 was 50%, a proportion of C18O18O in CO2 at a gas-phase outlet of the secondary gas-liquid separation device 10 was 82%, and a proportion of C18O18O in CO2 at a gas-phase outlet of the tertiary gas-liquid separation device 14 was 95%.
This application example provides a preparation method for isotope-labeled carbon dioxide. In the preparation method, the system provided in Example 1 was used. This application example differs from Application Example 1 in that the catalytic material in the primary oxygen-exchange reaction device 4, the secondary oxygen-exchange reaction device 8, and the tertiary oxygen-exchange reaction device 12 are replaced by anatase titanium dioxide with an equal amount.
In this application example, a proportion of C18O18O in CO2 at a gas-phase outlet of the primary gas-liquid separation device 6 was 48%, a proportion of C18O18O in CO2 at a gas-phase outlet of the secondary gas-liquid separation device 10 was 78%, and a proportion of C18O18O in CO2 at a gas-phase outlet of the tertiary gas-liquid separation device 14 was 90%.
This comparative application example provides a preparation method for isotope-labeled carbon dioxide. In the preparation method, the system provided in Example 1 was used. This comparative application example differs from Application Example 1 in that no catalytic material is arranged in the primary oxygen-exchange reaction device 4, the secondary oxygen-exchange reaction device 8, or the tertiary oxygen-exchange reaction device 12.
In this comparative application example, no catalytic material is arranged in the oxygen-exchange reaction devices, heavy-oxygen water cannot undergo the oxygen-exchange reaction with CO2, and the oxygen in CO2 is not replaced by O-18.
As can be seen from Table 1, based on the system and the method provided by the present application, the preparation of the isotope-labeled carbon dioxide can be realized by oxygen exchange with heavy-oxygen water; the concentration of C18O2 after the secondary oxygen exchange can reach more than or equal to 72%; after the tertiary oxygen exchange, the concentration of C18O2 can increase to more than or equal to 88%, the reaction efficiency is high, and the preparation purity is high; the utilization rate of the raw material heavy-oxygen water is high, and the heavy-oxygen water after the reaction is collected in the storage device and can be reused.
In conclusion, the system provided by the present application has a simple structure, by adopting the heavy-oxygen water which has a wide source and low cost as an oxygen isotope source and utilizing the oxygen-exchange reaction, the replacement of oxygen-16 in normal carbon dioxide by oxygen-18 in heavy-oxygen water can be achieved to obtain the oxygen-18 labeled carbon dioxide product. The process is simple and pollution-free, the utilization rate of oxygen isotope is high, the conditions of separation and purification are mild, and the system has good economic benefits and application prospects.
The applicant declares that the above is only the embodiments of the present application, but the protection scope of the present application is not limited thereto. Those skilled in the art should understand that any change or replacement, which can be easily thought of by a person skilled in the art within the scope of the technology disclosed in the present application, shall fall within the protection scope and disclosure scope of the present application.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202311640673.9 | Jan 2023 | CN | national |
