SYSTEM FOR PREPARING ISOTOPE-LABELED CARBON DIOXIDE AND METHOD THEREFOR
20240239665 ยท 2024-07-18
Assignee
Inventors
Cpc classification
B01J2219/00103
PERFORMING OPERATIONS; TRANSPORTING
B01J19/0013
PERFORMING OPERATIONS; TRANSPORTING
C01P2006/88
CHEMISTRY; METALLURGY
International classification
B01J19/24
PERFORMING OPERATIONS; TRANSPORTING
B01J19/00
PERFORMING OPERATIONS; TRANSPORTING
Abstract
Provided are a system for preparing isotope-labeled carbon dioxide and a method therefor. The preparation method comprises: vaporizing heavy-oxygen water and mixing the heavy-oxygen water with carbon dioxide, and subjecting the heavy-oxygen water and the carbon dioxide to an oxygen-exchange reaction by catalyzing them with a catalytic material, and performing gas-liquid separation after the reaction to obtain the isotope-labeled carbon dioxide. The system provided by the present application has a simple structure, and 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.
Claims
1. A system for preparing isotope-labeled carbon dioxide, comprising: 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 preparation unit comprises a heating vaporization device, an oxygen-exchange reaction device, and a gas-liquid separation device which are connected in sequence, and a catalytic material is arranged in the oxygen-exchange reaction device; an inlet of the heating vaporization device is connected to the raw material storage device for heavy-oxygen water and the raw material storage device for carbon dioxide, respectively; a gas-phase outlet of the gas-liquid separation device is connected to the product storage device, and a liquid-phase outlet of the gas-liquid separation device is connected to the recovery and storage device for heavy-oxygen water.
2. The system according to claim 1, wherein the system comprises at least one preparation unit.
3. The system according to claim 2, wherein in a case where the system comprises two or more preparation units, the inlet of the heating vaporization device in 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.
4. The system according to claim 2, wherein in a case where the system comprises two or more preparation units, a heat-exchange device is further arranged between two adjacent preparation units; a hot-medium inlet of the heat-exchange device is connected to an outlet of the oxygen-exchange reaction device in a next preparation unit along the flow direction of materials in the system; a cold-medium inlet of the heat-exchange device is connected to a gas-phase outlet of the gas-liquid separation device in a previous preparation unit; a hot-medium outlet of the heat-exchange device is connected to an inlet of the gas-liquid separation device in a next preparation unit; a cold-medium outlet of the heat-exchange device is connected to an inlet of the heating vaporization device in a next preparation unit.
5. The system according to claim 1, wherein the catalytic material comprises any one or a combination of at least two of ?-Al.sub.2O.sub.3, CeO.sub.2, or anatase titanium dioxide.
6. A preparation method for isotope-labeled carbon dioxide, which adopts the system according to claim 1.
7. The preparation method according to claim 6, wherein 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 .sup.16O in the carbon dioxide is replaced by .sup.18O in the heavy-oxygen water to generate isotope-labeled carbon dioxide, and .sup.18O in the heavy-oxygen water is replaced by .sup.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.
8. The preparation method according to claim 7, wherein a molar ratio of the heavy-oxygen water to the carbon dioxide in step (1) is (2-5):1.
9. The preparation method according to claim 7, wherein the vaporization in step (1) is performed at a temperature of 100-300? C.
10. The preparation method according to claim 7, wherein the oxygen-exchange reaction in step (2) is performed at a volumetric space velocity of 5000-100000 h.sup.?1.
11. The preparation method according to claim 7, wherein the liquefaction in step (3) is performed at a temperature of ?10? C. to 20? C.
Description
BRIEF DESCRIPTION OF DRAWINGS
[0033]
REFERENCE LIST
[0034] 1raw material storage device for heavy-oxygen water; 2raw material storage device for carbon dioxide; 3primary heating vaporization device; 4primary oxygen-exchange reaction device; 5catalytic material; 6primary gas-liquid separation device; 7secondary heating vaporization device; 8secondary oxygen-exchange reaction device; 9 heat-exchange device; 10secondary gas-liquid separation device; 11tertiary heating vaporization device; 12tertiary oxygen-exchange reaction device; 13heat-exchange device; 14tertiary gas-liquid separation device; 15product storage device; and 16recovery and storage device for heavy-oxygen water.
DETAILED DESCRIPTION
[0035] 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.
Example 1
[0036] The example provides a system for preparing isotope-labeled carbon dioxide, as shown in
Example 2
[0047] 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; [0048] the primary preparation unit comprises a primary heating vaporization device 3, a primary oxygen-exchange reaction device 4, and a primary gas-liquid separation device 6 which are connected in sequence; [0049] the secondary preparation unit comprises a secondary heating vaporization device 7, a secondary oxygen-exchange reaction device 8, and a secondary gas-liquid separation device 10, and the secondary heating vaporization device 7 is connected to the secondary oxygen-exchange reaction device 8; [0050] the primary oxygen-exchange reaction device 4 and the secondary oxygen-exchange reaction device 8 are both provided with a catalytic material 5, and the catalytic material 5 is ?-Al.sub.2O.sub.3; [0051] the raw material storage device for heavy-oxygen water 1 is connected to the primary heating vaporization device 3 and the secondary heating vaporization device 7, respectively; [0052] the raw material storage device for carbon dioxide 2 is connected to the primary heating vaporization device 3; [0053] a cold-medium inlet of the heat-exchange device 9 is connected to a gas-phase outlet of the primary gas-liquid separation device 6; a hot-medium inlet of the heat-exchange device 9 is connected to the secondary oxygen-exchange reaction device 8; a hot-medium outlet of the heat-exchange device 9 is connected to the secondary gas-liquid separation device 10; a cold-medium outlet of the heat-exchange device 9 is connected to the secondary heating vaporization device 7; [0054] the product storage device 15 is connected to a gas-phase outlet of the secondary gas-liquid separation device 10; [0055] the recovery and storage device for heavy-oxygen water 16 is connected to liquid-phase outlets of the primary gas-liquid separation device 6 and the secondary gas-liquid separation device 10, respectively.
Application Example 1
[0056] 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:
[0057] (1) heavy-oxygen water (H.sub.2.sup.18O 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 (CO.sub.2) 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.;
[0058] (2) the mixed gas of H.sub.2.sup.18O and CO.sub.2 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.sup.?1; and under the action of the catalytic material ?-Al.sub.2O.sub.3, H.sub.2.sup.18O was decomposed, and reacted with CO.sub.2 adsorbed on the material for oxygen exchange, where .sup.16O in the CO.sub.2 was replaced by .sup.18O in the H.sub.2.sup.18O to generate oxygen-18 labeled carbon dioxide (C.sup.18O.sup.16O and C.sup.18O.sup.18O), and .sup.18O in the H.sub.2.sup.18O was replaced by .sup.16O to generate H.sub.2.sup.16O;
[0059] (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 (H.sub.2.sup.18O and H.sub.2.sup.16O) entered a recovery and storage device for heavy-oxygen water 16, and a separated gas-phase carbon dioxide (C.sup.16O.sup.16O, C.sup.18O.sup.16O, and C.sup.18O.sup.18O) was heated to 80? C. by a heat-exchange device 9; and
[0060] (4) the gas-phase carbon dioxide (C.sup.16O.sup.16O, C.sup.18O.sup.16O, and C.sup.18O.sup.18O) 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.
[0061] In this application example, a proportion of C.sup.18O.sup.18O in CO.sub.2 at a gas-phase outlet of the primary gas-liquid separation device 6 was 52%, a proportion of C.sup.18O.sup.18O in CO.sub.2 at a gas-phase outlet of the secondary gas-liquid separation device 10 was 84%, and a proportion of C.sup.18O.sup.18O in CO.sub.2 at a gas-phase outlet of the tertiary gas-liquid separation device 14 was 98%.
Application Example 2
[0062] 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:
[0063] (1) heavy-oxygen water (H.sub.2.sup.18O 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 (CO.sub.2) 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.;
[0064] (2) the mixed gas of H.sub.2.sup.18O and CO.sub.2 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.sup.?1; and under the action of the catalytic material ?-Al.sub.2O.sub.3, H.sub.2.sup.18O was decomposed, and reacted with CO.sub.2 adsorbed on the material for oxygen exchange, where .sup.16O in the CO.sub.2 was replaced by .sup.18O in the H.sub.2.sup.18O to generate oxygen-18 labeled carbon dioxide (C.sup.18O.sup.16O and C.sup.18O.sup.18O), and .sup.18O in the H.sub.2.sup.18O was replaced by .sup.16O to generate H.sub.2.sup.16O;
[0065] (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 (H.sub.2.sup.18O and H.sub.2.sup.16O) entered a recovery and storage device for heavy-oxygen water 16, and a separated gas phase carbon dioxide (C.sup.16O.sup.16O, C.sup.18O.sup.16O, and C.sup.18O.sup.18O) was heated to 80? C. by a heat-exchange device 9; and
[0066] (4) the gas phase carbon dioxide (C.sup.16O.sup.16O, C.sup.18O.sup.16O, and C.sup.18O.sup.18O) 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.
[0067] In this application example, a proportion of C.sup.18O.sup.18O in CO.sub.2 at a gas-phase outlet of the primary gas-liquid separation device 6 was 45%, a proportion of C.sup.18O.sup.18O in CO.sub.2 at a gas-phase outlet of the secondary gas-liquid separation device 10 was 72%, and a proportion of C.sup.18O.sup.18O in CO.sub.2 at a gas-phase outlet of the tertiary gas-liquid separation device 14 was 88%.
Application Example 3
[0068] 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:
[0069] (1) heavy-oxygen water (H.sub.2.sup.18O 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 (CO.sub.2) 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.;
[0070] (2) the mixed gas of H.sub.2.sup.18O and CO.sub.2 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.sup.?1; and under the action of the catalytic material ?-Al.sub.2O.sub.3, H.sub.2.sup.18O was decomposed, and reacted with CO.sub.2 adsorbed on the material for oxygen exchange, where .sup.16O in the CO.sub.2 was replaced by .sup.18O in the H.sub.2.sup.18O to generate oxygen-18 labeled carbon dioxide (C.sup.18O.sup.16O and C.sup.18O.sup.18O), and .sup.18O in the H.sub.2.sup.18O was replaced by .sup.16O to generate H.sub.2.sup.16O;
[0071] (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 (H.sub.2.sup.18O and H.sub.2.sup.16O) entered a recovery and storage device for heavy-oxygen water 16, and a separated gas phase carbon dioxide (C.sup.16O.sup.16O, C.sup.18O.sup.16O, and C.sup.18O.sup.18O) was heated to 80? C. by a heat-exchange device 9; and
[0072] (4) the gas phase carbon dioxide (C.sup.16O.sup.16O, C.sup.18O.sup.16O, and C.sup.18O.sup.18O) 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.
[0073] In this application example, a proportion of C.sup.18O.sup.18O in CO.sub.2 at a gas-phase outlet of the primary gas-liquid separation device 6 was 64%, a proportion of C.sup.18O.sup.18O in CO.sub.2 at a gas-phase outlet of the secondary gas-liquid separation device 10 was 87%, and a proportion of C.sup.18O.sup.18O in CO.sub.2 at a gas-phase outlet of the tertiary gas-liquid separation device 14 was 99%.
Application Example 4
[0074] 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.
[0075] In this application example, a proportion of C.sup.18O.sup.18O in CO.sub.2 at a gas-phase outlet of the primary gas-liquid separation device 6 was 40%, a proportion of C.sup.18O.sup.18O in CO.sub.2 at a gas-phase outlet of the secondary gas-liquid separation device 10 was 75%, and a proportion of C.sup.18O.sup.18O in CO.sub.2 at a gas-phase outlet of the tertiary gas-liquid separation device 14 was 96%.
Application Example 5
[0076] 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 CeO.sub.2 with an equal amount.
[0077] In this application example, a proportion of C.sup.18O.sup.18O in CO.sub.2 at a gas-phase outlet of the primary gas-liquid separation device 6 was 50%, a proportion of C.sup.18O.sup.18O in CO.sub.2 at a gas-phase outlet of the secondary gas-liquid separation device 10 was 82%, and a proportion of C.sup.18O.sup.18O in CO.sub.2 at a gas-phase outlet of the tertiary gas-liquid separation device 14 was 95%.
Application Example 6
[0078] 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.
[0079] In this application example, a proportion of C.sup.18O.sup.18O in CO.sub.2 at a gas-phase outlet of the primary gas-liquid separation device 6 was 48%, a proportion of C.sup.18O.sup.18O in CO.sub.2 at a gas-phase outlet of the secondary gas-liquid separation device 10 was 78%, and a proportion of C.sup.18O.sup.18O in CO.sub.2 at a gas-phase outlet of the tertiary gas-liquid separation device 14 was 90%.
Comparative Application Example 1
[0080] 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.
[0081] 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 CO.sub.2, and the oxygen in CO.sub.2 is not replaced by O-18.
TABLE-US-00001 TABLE 1 Proportion of C.sup.18O.sup.18O in product (%) Utilization Primary Secondary Tertiary rate of oxygen oxygen oxygen heavy-oxygen exchange exchange exchange water (%) Application 52 84 98 90 Example 1 Application 45 72 88 93 Example 2 Application 64 87 99 84 Example 3 Application 40 75 96 86 Example 4 Application 50 82 95 86 Example 5 Application 48 78 90 85 Example 6 Comparative 0 0 0 0 Application Example 1
[0082] 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 C.sup.18O.sub.2 after the secondary oxygen exchange can reach more than or equal to 72%; after the tertiary oxygen exchange, the concentration of C.sup.18O.sub.2 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.
[0083] 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.
[0084] 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.