A system and method for producing isotopically labeled carbon dioxide

Abstract

The application provides a device system and a method for preparing isotopically labeled carbon dioxide, and the preparation method comprises the following steps: vaporizing heavy oxygen water, mixing the heavy oxygen water with carbon dioxide, catalyzing through a catalytic material, carrying out oxygen exchange reaction between the heavy oxygen water and the carbon dioxide, carrying out gas-liquid separation after the reaction, and obtaining isotopically labeled carbon dioxide. The device system provided by the application has the advantages of simple structure, wide source and low price of heavy oxygen water as an oxygen isotope source, oxygen exchange, replacement of oxygen-16 of conventional carbon dioxide by oxygen-18 of the heavy oxygen water, oxygen-18 isotopically labeled carbon dioxide products, simple process, green and pollution-free, high oxygen isotope utilization rate, mild separation and purification conditions, good economic benefits and application prospect.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of carbon dioxide preparation, and particularly relates to a device system and a method for preparing isotopically labeled carbon dioxide. BACKGROUND

[0002] In the conversion reaction process of carbon dioxide, isotopic tracing experiment is an important means to study the CO2 conversion pathway and reaction mechanism, and oxygen isotope labeled carbon dioxide is the main material for isotopic experiment. However, oxygen isotope labeled carbon dioxide is very expensive due to the complex preparation and separation and purification process, which limits the application of oxygen isotope labeled carbon dioxide in related research fields.

[0003] CN114436260A discloses a device and a method for preparing oxygen isotope labeled carbon monoxide and carbon dioxide. Oxygen isotope labeled oxalic acid is heated in a reaction kettle to decompose the oxalic acid to obtain oxygen isotope labeled CO2, CO and H2O, and then oxygen isotope labeled CO2, CO and H2O are collected in different temperatures by a collection bottle and a refrigeration device. The method has simple preparation process and product separation and purification process, high oxygen isotope utilization rate, and can obtain carbon dioxide product with O-18 abundance greater than 95%. However, the method uses oxygen isotope labeled oxalic acid as an isotopic source, which is expensive itself and has harsh separation and purification conditions, and the refrigeration temperature needs to be below-100℃.

[0004] Therefore, it is of great significance to develop a simple, green, efficient and low-cost device system and method for preparing oxygen-18 isotope labeled carbon dioxide to meet the application needs of related research fields. SUMMARY

[0005] The purpose of the present application is to provide a device system and a method for preparing isotopically labeled carbon dioxide, which has a wide source of raw materials, low cost, mild preparation conditions, simple process, good economic benefits and application prospect.

[0006] To achieve this purpose, the present application adopts the following technical solutions:

[0007] In a first aspect, the present application provides a device system for preparing isotopically labeled carbon dioxide, which comprises a preparation unit, a heavy oxygen water raw material storage device, a carbon dioxide raw material storage device, a product storage device and a heavy oxygen water recovery storage device.

[0008] The preparation unit comprises a heating vaporization device, an oxygen exchange reaction device and a gas-liquid separation device connected in sequence, and the oxygen exchange reaction device is provided with a catalytic material;

[0009] The inlet of the heating vaporization device is connected with the heavy oxygen water raw material storage device and the carbon dioxide raw material storage device respectively.

[0010] The gas phase outlet of the gas-liquid separation device is connected with the product storage device, and the liquid phase outlet of the gas-liquid separation device is connected with the heavy oxygen water recovery storage device.

[0011] The device system provided by the application has simple structure, uses the widely available and low-cost heavy oxygen water as the oxygen isotope source, realizes the oxygen-18 substitution of oxygen-16 of the conventional carbon dioxide by using the oxygen exchange, thereby obtaining the oxygen-18 isotope labeled carbon dioxide product, and has simple process, no pollution, high oxygen isotope utilization rate, mild separation and purification conditions, good economic benefits and good application prospect.

[0012] Preferably, the device system comprises at least one preparation unit.

[0013] The device system provided by the application can flexibly set the preparation unit according to the product purity requirement, is convenient to set, and meets different product requirements.

[0014] Preferably, when the device system comprises two or more preparation units, the inlet of the heating vaporization device of the rear preparation unit is connected with the heavy oxygen water raw material storage device and the gas phase outlet of the gas-liquid separation device of the front preparation unit respectively along the material flow direction in the device system.

[0015] Preferably, when the device system comprises two or more preparation units, a heat exchange device is further arranged between the adjacent two preparation units.

[0016] The heat medium inlet of the heat exchange device is connected with the outlet of the oxygen exchange reaction device of the rear preparation unit along the material flow direction in the device system.

[0017] The cold medium inlet of the heat exchange device is connected with the gas phase outlet of the gas-liquid separation device of the front preparation unit.

[0018] The heat medium outlet of the heat exchange device is connected with the inlet of the gas-liquid separation device of the rear preparation unit.

[0019] The cold medium outlet of the heat exchange device is connected with the inlet of the heating vaporization device of the rear preparation unit.

[0020] Preferably, the catalytic material comprises any one or a combination of at least two of γ-Al2O3, CeO2 or anatase titanium dioxide, and a typical but non-limiting combination comprises 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.

[0021] In a second aspect, the present application provides a method for preparing isotopically labeled carbon dioxide, which method uses the device system of the first aspect.

[0022] Preferably, the method comprises the following steps:

[0023] (1) vaporizing heavy-oxygen water and mixing it with carbon dioxide to obtain a mixed gas;

[0024] (2) subjecting the mixed gas obtained in step (1) to catalysis by a catalytic material, so that oxygen exchange occurs between the heavy-oxygen water and the carbon dioxide, the 16 O in the carbon dioxide is replaced by the 18 O in the heavy-oxygen water, to produce isotopically labeled carbon dioxide, and the 18 O in the heavy-oxygen water is replaced by 16 O;

[0025] (3) liquefying the heavy-oxygen water after the reaction and subjecting it to gas-liquid separation from the carbon dioxide after the reaction, to obtain isotopically labeled carbon dioxide.

[0026] Preferably, the molar ratio of the heavy-oxygen water to the carbon dioxide in step (1) is (2-5): 1, for example, it can be 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1 or 5:1, but is not limited to the listed values, and other values not listed within the range of values are also applicable.

[0027] Preferably, the temperature of vaporization in step (1) is 100-300°C, for example, it can be 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, but is not limited to the listed values, and other values not listed within the range of values are also applicable.

[0028] Preferably, the volume space velocity of the oxygen exchange reaction in step (2) is 5000-100000 h -1 , for example, it can be 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 -1but are not limited to the recited numerical values, and other non-recited numerical values within the numerical range are also applicable.

[0029] Preferably, the temperature of the liquefaction in step (3) is -10℃ to 20℃, for example, can be -10℃, -5℃, 0℃, 5℃, 10℃, 15℃ or 20℃, but are not limited to the recited numerical values, and other non-recited numerical values within the numerical range are also applicable.

[0030] Compared with the prior art, the present application has the following beneficial effects:

[0031] The device system provided by the present application has simple structure, uses widely-sourced and inexpensive heavy oxygen water as an oxygen isotope source, realizes oxygen-18 substitution of oxygen-16 of conventional carbon dioxide by oxygen exchange, thereby obtaining oxygen-18 isotope-labeled carbon dioxide product, and has simple process, no pollution, high oxygen isotope utilization rate, mild separation and purification conditions, good economic benefits and good application prospect. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 is a device system for preparing isotopically labeled carbon dioxide provided by Example 1;

[0033] wherein 1 is a heavy oxygen water raw material storage device; 2 is a carbon dioxide raw material storage device; 3 is a first-stage heating vaporization device; 4 is a first-stage oxygen exchange reaction device; 5 is a catalytic material; 6 is a first-stage gas-liquid separation device; 7 is a second-stage heating vaporization device; 8 is a second-stage oxygen exchange reaction device; 9 is a heat exchange device; 10 is a second-stage gas-liquid separation device; 11 is a third-stage heating vaporization device; 12 is a third-stage oxygen exchange reaction device; 13 is a heat exchange device; 14 is a third-stage gas-liquid separation device; 15 is a product storage device; and 16 is a heavy oxygen water recovery storage device. DETAILED DESCRIPTION

[0034] The technical solutions of the present application are further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only used to help understand the present application and should not be regarded as specific limitations on the present application.

[0035] Example 1

[0036] This embodiment provides a device system for preparing isotopically labeled carbon dioxide as shown in Figure 1 The device system comprises a first-stage preparation unit, a second-stage preparation unit, a third-stage preparation unit, a heavy oxygen water raw material storage device 1, a carbon dioxide raw material storage device 2, a product storage device 15, a heavy oxygen water recovery storage device 16, a heat exchange device 9 and a heat exchange device 13.

[0037] 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 connected in sequence;

[0038] 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, wherein the secondary heating vaporization device 7 and the secondary oxygen exchange reaction device 8 are connected;

[0039] The tertiary preparation unit comprises a tertiary heating vaporization device 11, a tertiary oxygen exchange reaction device 12 and a secondary gas-liquid separation device 14, wherein the tertiary heating vaporization device 11 and the tertiary oxygen exchange reaction device 12 are connected;

[0040] The primary oxygen exchange reaction device 4, the secondary oxygen exchange reaction device 8 and the tertiary oxygen exchange reaction device 12 are all provided with a catalytic material 5, and the catalytic material 5 is γ-Al2O3;

[0041] The heavy oxygen water raw material storage device 1 is connected with the primary heating vaporization device 3, the secondary heating vaporization device 7 and the tertiary heating vaporization device 11 respectively;

[0042] The carbon dioxide raw material storage device 2 is connected with the primary heating vaporization device 3;

[0043] The cold medium inlet of the heat exchange device 9 is connected with the gas phase outlet of the primary gas-liquid separation device 6, the hot medium inlet of the heat exchange device 9 is connected with the secondary oxygen exchange reaction device 8, the hot medium outlet of the heat exchange device 9 is connected with the secondary gas-liquid separation device 10, and the cold medium outlet of the heat exchange device 9 is connected with the secondary heating vaporization device 7;

[0044] The cold medium inlet of the heat exchange device 13 is connected with the gas phase outlet of the secondary gas-liquid separation device 10, the hot medium inlet of the heat exchange device 13 is connected with the tertiary oxygen exchange reaction device 12, the hot medium outlet of the heat exchange device 13 is connected with the tertiary gas-liquid separation device 14, and the cold medium outlet of the heat exchange device 13 is connected with the tertiary heating vaporization device 11;

[0045] The product storage device 15 is connected with the gas phase outlet of the tertiary gas-liquid separation device 14;

[0046] The heavy oxygen water recovery storage device 16 is connected with the liquid phase outlets of the primary gas-liquid separation device 6, the secondary gas-liquid separation device 10 and the tertiary gas-liquid separation device 14 respectively.

[0047] Example 2

[0048] The embodiment provides a device system for preparing isotopically labeled carbon dioxide, which comprises a primary preparation unit, a secondary preparation unit, a heavy oxygen water raw material storage device 1, a carbon dioxide raw material storage device 2, a product storage device 15, a heavy oxygen water recovery storage device 16 and a heat exchange device 9.

[0049] 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 connected in sequence;

[0050] 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 and the secondary oxygen exchange reaction device 8 are connected;

[0051] 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 γ-Al2O3;

[0052] The heavy-oxygen water raw material storage device 1 is connected with the primary heating vaporization device 3 and the secondary heating vaporization device 7 respectively;

[0053] The carbon dioxide raw material storage device 2 is connected with the primary heating vaporization device 3;

[0054] The cold medium inlet of the heat exchange device 9 is connected with the gas phase outlet of the primary gas-liquid separation device 6, the hot medium inlet of the heat exchange device 9 is connected with the secondary oxygen exchange reaction device 8, the hot medium outlet of the heat exchange device 9 is connected with the secondary gas-liquid separation device 10, and the cold medium outlet of the heat exchange device 9 is connected with the secondary heating vaporization device 7;

[0055] The product storage device 15 is connected with the gas phase outlet of the secondary gas-liquid separation device 10;

[0056] The heavy-oxygen water recovery storage device 16 is connected with the liquid phase outlets of the primary gas-liquid separation device 6 and the secondary gas-liquid separation device 10 respectively.

[0057] Application Example 1

[0058] The application example provides a preparation method of isotopically labeled carbon dioxide, and the preparation method uses the device system provided in the embodiment 1, and the preparation method comprises the following steps:

[0059] (1) heavy-oxygen water (H2 18 O, in the form of liquid phase) provided by the heavy-oxygen water raw material storage device 1 is input into the primary heating vaporization device 3, and the heavy-oxygen water is vaporized into a gas phase, carbon dioxide (CO2) provided by the carbon dioxide raw material storage device 2 is mixed with the gas phase heavy-oxygen water, the molar ratio of the heavy-oxygen water to the carbon dioxide is 3:1, and the temperature of the mixed gas at the outlet of the primary heating vaporization device 3 is 120℃;

[0060] (2) the mixed gas H2 18 O and CO2 enters the primary oxygen exchange reaction device 4, the reaction temperature of the primary oxygen exchange reaction device 4 is 110℃, and the volume space velocity is 10000h -1H2 18 O is decomposed and exchanges oxygen with CO2 adsorbed on the material, and C 16 O in CO2 is replaced by H2 18 O 18 O, to generate oxygen-18 isotope-labeled carbon dioxide (C 18 O 16 O, C 18 O 18 O), H2 18 O in H2 18 O is replaced by C 16 O, to generate H2 16 O;

[0061] (3) The gas after the oxygen exchange reaction is cooled by the gas-liquid separation device 6, and the cooling temperature is -3℃. The separated liquid phase water (H2 18 O and H2 16 O) enters the heavy oxygen water recovery storage device 16, and the separated gas phase carbon dioxide (C 16 O 16 O, C 18 O 16 O, C 18 O 18 O) is raised in temperature to 80℃ by the heat exchange device 9.

[0062] (4) The gas phase carbon dioxide (C 16 O 16 O, C 18 O 16 O, C 18 O 18 O) after the first oxygen exchange reaction is sequentially subjected to the second preparation unit and the third preparation unit, and the same vaporization, oxygen exchange reaction and gas-liquid separation process as steps (1) to (3) are performed, to obtain the isotope-labeled carbon dioxide product into the product storage device 15.

[0063] In the application example, the proportion of C 18 O 18 O in the CO2 at the gas phase outlet of the first gas-liquid separation device 6 is 52%, the proportion of C 18 O 18 O in the CO2 at the gas phase outlet of the second gas-liquid separation device 10 is 84%, and the proportion of C 18 O 18 O in the CO2 at the gas phase outlet of the third gas-liquid separation device 14 is 98%.

[0064] Application Example 2

[0065] This application example provides a method for preparing isotope-labeled carbon dioxide. The preparation method uses the apparatus system provided in Example 1 and includes the following steps:

[0066] (1) Heavy oxygen water (H2) is supplied by the heavy oxygen water raw material storage device 1. 18 O (existing in liquid form) is fed into the first-stage heating and vaporization device 3, where the heavy oxygen water is vaporized into a gaseous phase. Carbon dioxide (CO2) is provided by the carbon dioxide raw material storage device 2. The gaseous heavy oxygen water and carbon dioxide are mixed, with a molar ratio of heavy oxygen water to carbon dioxide of 2:1. The temperature of the mixed gas at the outlet of the first-stage heating and vaporization device 3 is 100°C.

[0067] (2) Mixed gas H2 18 O and CO2 enter the first-stage oxygen exchange reactor 4. The reaction temperature of the first-stage oxygen exchange reactor 4 is 110℃, and the volume hourly space velocity is 5000 h⁻¹. -1 Under the action of the catalytic material γ-Al2O3, H2 18 O is decomposed and undergoes an oxygen exchange reaction with CO2 adsorbed on the material. The CO2 contains... 16 O was H2 18 O 18 O substitution produces oxygen-18 isotope-labeled carbon dioxide (C₂). 18 O 16 O, C 18 O 18 O), H2 18 O 18 O was replaced with 16 O, generating H2 16 O;

[0068] (3) The gas after the oxygen exchange reaction is cooled by the gas-liquid separator 6 at a temperature of -10℃, and the separated liquid phase is water (H2). 18 O and H2 16 O) enters the heavy oxygen water recovery and storage device 16, where the separated gaseous carbon dioxide (C) 16 O 16 O, C 18 O 16 O, C 18 O 18 O) The temperature rises to 80℃ after passing through heat exchanger 9;

[0069] (4) Gas-phase carbon dioxide (C) after primary oxygen exchange reaction 16 O 16 O, C 18 O 16 O, C 18 O 18O) and sequentially through the secondary preparation unit and the tertiary preparation unit, the same vaporization, oxygen exchange reaction and gas-liquid separation process as steps (1) to (3) are carried out to obtain isotopically labeled carbon dioxide product into the product storage device 15.

[0070] In the application example, the proportion of C 18 O 18 O in the CO2 in the gas phase outlet of the primary gas-liquid separation device 6 is 45%, the proportion of C 18 O 18 O in the CO2 in the gas phase outlet of the secondary gas-liquid separation device 10 is 72%, and the proportion of C 18 O 18 O in the CO2 in the gas phase outlet of the tertiary gas-liquid separation device 14 is 88%.

[0071] Application Example 3

[0072] The application example provides a preparation method of isotopically labeled carbon dioxide, which uses the device system provided in Example 1, and the preparation method comprises the following steps:

[0073] (1) The heavy oxygen water (H2 18 O, in liquid phase) provided by the heavy oxygen water raw material storage device 1 is introduced into the primary heating vaporization device 3, and the heavy oxygen water is vaporized into a gas phase, the carbon dioxide (CO2) provided by the carbon dioxide raw material storage device 2 is mixed with the gaseous heavy oxygen water, the molar ratio of the heavy oxygen water to the carbon dioxide is 5:1, and the temperature of the mixed gas at the outlet of the primary heating vaporization device 3 is 300°C;

[0074] (2) The mixed gas H2 18 O and CO2 enters the primary oxygen exchange reaction device 4, the reaction temperature of the primary oxygen exchange reaction device 4 is 110°C, and the volume space velocity is 100000 h -1 Under the action of the catalytic material γ-Al2O3, H2 18 O is decomposed, and oxygen exchange reaction occurs between H2 16 O and the CO2 adsorbed on the material, and the C 18 O in the CO2 is replaced by the O in the H2 18 O to generate oxygen-18 isotopically labeled carbon dioxide (C 18 O 16 O, C 18 O 18 O), and the O in the H2 18 O is replaced by O to generate H2 18 O; 16 O; 16 O.

[0075] (3) The gas after the oxygen exchange reaction is cooled through the gas-liquid separation device 6, the cooling temperature is 20°C, and the separated liquid phase water (H218 O and H2 16 O) into the heavy oxygen water recovery storage device 16, and the separated gaseous phase carbon dioxide (C 16 O 16 O, C 18 O 16 O, C 18 O 18 O) is raised in temperature to 80°C by the heat exchange device 9;

[0076] (4) the gaseous phase carbon dioxide (C 16 O 16 O, C 18 O 16 O, C 18 O 18 O) is sequentially subjected to a second preparation unit and a third preparation unit, and the same vaporization, oxygen exchange reaction and gas-liquid separation processes as steps (1) to (3) are performed, to obtain isotopically labeled carbon dioxide products into the product storage device 15.

[0077] In this application example, the proportion of C 18 O 18 O in the gaseous phase CO2 outlet of the first gas-liquid separation device 6 is 64%, the proportion of C 18 O 18 O in the gaseous phase CO2 outlet of the second gas-liquid separation device 10 is 87%, and the proportion of C 18 O 18 O in the gaseous phase CO2 outlet of the third gas-liquid separation device 14 is 99%.

[0078] Application Example 4

[0079] This application example provides a preparation method of isotopically labeled carbon dioxide, which uses the device system provided in Example 1. Compared with Application Example 1, the molar ratio of heavy oxygen water to carbon dioxide in the first heating vaporization device 3, the second heating vaporization device 7 and the third heating vaporization device is 2:1, 3:1 and 4:1 respectively, and the rest is the same as Application Example 1.

[0080] In this application example, the proportion of C 18 O 18 O in the gaseous phase CO2 outlet of the first gas-liquid separation device 6 is 40%, the proportion of C 18 O 18 O in the gaseous phase CO2 outlet of the second gas-liquid separation device 10 is 75%, and the proportion of C 18 O 18 O in the gaseous phase CO2 outlet of the third gas-liquid separation device 14 is 96%.

[0081] Application Example 5

[0082] The application example provides a preparation method of isotopically labeled carbon dioxide, which uses the device system provided in the embodiment 1, and compared with the application example 1, the catalytic materials in the first-stage oxygen exchange reaction device 4, the second-stage oxygen exchange reaction device 8 and the third-stage oxygen exchange reaction device 12 are replaced by CeO2 in equal amounts.

[0083] In the application example, the proportion of C 18 O 18 O in the CO2 in the gas phase outlet of the first-stage gas-liquid separation device 6 is 50%, the proportion of C 18 O 18 O in the CO2 in the gas phase outlet of the second-stage gas-liquid separation device 10 is 82%, and the proportion of C 18 O 18 O in the CO2 in the gas phase outlet of the third-stage gas-liquid separation device 14 is 95%.

[0084] Application example 6

[0085] The application example provides a preparation method of isotopically labeled carbon dioxide, which uses the device system provided in the embodiment 1, and compared with the application example 1, the catalytic materials in the first-stage oxygen exchange reaction device 4, the second-stage oxygen exchange reaction device 8 and the third-stage oxygen exchange reaction device 12 are replaced by CeO2 in equal amounts.

[0086] In the application example, the proportion of C 18 O 18 O in the CO2 in the gas phase outlet of the first-stage gas-liquid separation device 6 is 48%, the proportion of C 18 O 18 O in the CO2 in the gas phase outlet of the second-stage gas-liquid separation device 10 is 78%, and the proportion of C 18 O 18 O in the CO2 in the gas phase outlet of the third-stage gas-liquid separation device 14 is 90%.

[0087] Comparative application example 1

[0088] The application example provides a preparation method of isotopically labeled carbon dioxide, which uses the device system provided in the embodiment 1, and compared with the application example 1, the catalytic materials in the first-stage oxygen exchange reaction device 4, the second-stage oxygen exchange reaction device 8 and the third-stage oxygen exchange reaction device 12 are replaced by CeO2 in equal amounts.

[0089] In the comparative application example, there is no catalytic material in the oxygen exchange reaction device, and the heavy oxygen water cannot react with CO2, so the oxygen in the CO2 is not replaced by O-18.

[0090] Table 1

[0091]

[0092]

[0093] As can be seen from Table 1, the device system and method provided by the application can realize oxygen exchange preparation of isotopically labeled carbon dioxide by using heavy oxygen water, and the concentration of C 18 The concentration of O2 can reach more than 72%, and after the third oxygen exchange, the concentration can be increased to more than 88%, the reaction efficiency is high, the purity is high, the utilization rate of the reaction raw material heavy oxygen water is high, and the heavy oxygen water after the reaction can be collected in the storage device and reused.

[0094] In summary, the device system provided by the application has simple structure, uses widely available and cheap heavy oxygen water as an oxygen isotope source, realizes oxygen-18 substitution of oxygen-16 of conventional carbon dioxide by using oxygen exchange, thereby obtaining oxygen-18 isotopically labeled carbon dioxide product, and has simple process, no pollution, high oxygen isotope utilization rate, mild separation and purification conditions, good economic benefits and good application prospect.

[0095] The applicant declares that the above description is only a specific embodiment of the application, but the protection scope of the application is not limited thereto, and those skilled in the art should understand that any changes or replacements within the technical scope disclosed by the application can be easily thought of by those skilled in the art, and all fall within the protection scope and disclosure scope of the application.

Claims

1. An apparatus system for preparing isotope-labeled carbon dioxide, characterized in that, The device system includes: a preparation unit, a heavy oxygen water raw material storage device, a carbon dioxide raw material storage device, a product storage device, and a heavy oxygen water recovery and storage device; The preparation unit includes a heating vaporization device, an oxygen exchange reaction device, and a gas-liquid separation device connected in sequence. The oxygen exchange reaction device is equipped with a catalytic material. The catalytic material includes any one or a combination of at least two of γ-Al2O3, CeO2, or anatase titanium dioxide. The inlet of the heating vaporization device is connected to the heavy oxygen water raw material storage device and the carbon dioxide raw material storage device, respectively. The gas phase outlet of the gas-liquid separation device is connected to the product storage device, and the liquid phase outlet of the gas-liquid separation device is connected to the heavy oxygen water recovery and storage device.

2. The device system according to claim 1, characterized in that, The device system includes at least one preparation unit.

3. The device system according to claim 2, characterized in that, When the device system includes two or more preparation units, along the material flow direction within the device system, the inlet of the heating vaporization device in the later preparation unit is connected to the heavy oxygen water raw material storage device and the gas phase outlet of the gas-liquid separation device in the earlier preparation unit, respectively.

4. The device system according to claim 3, characterized in that, When the device system includes two or more preparation units, a heat exchange device is also provided between two adjacent preparation units; Along the direction of material flow within the system, the inlet of the heat exchange device is connected to the outlet of the oxygen exchange reaction device in the subsequent preparation unit. The cold medium inlet of the heat exchange device is connected to the gas phase outlet of the gas-liquid separation device in the preceding preparation unit; The heat medium outlet of the heat exchange device is connected to the inlet of the gas-liquid separation device in the subsequent preparation unit; The cold medium outlet of the heat exchange device is connected to the inlet of the heating vaporization device in the subsequent preparation unit.

5. A method for preparing isotope-labeled carbon dioxide, characterized in that, The preparation method uses the apparatus system described in any one of claims 1-4.

6. The preparation method according to claim 5, characterized in that, The preparation method includes the following steps: (1) After vaporizing the deoxygenated water, it is mixed with carbon dioxide to obtain a mixed gas; (2) The mixed gas obtained in step (1) is catalyzed by a catalytic material, and the deoxygenated water and carbon dioxide undergo an oxygen exchange reaction, and the carbon dioxide... 16 O in the oxygenated water 18 O substitution produces isotopically labeled carbon dioxide, which is present in deoxygenated water. 18 O was replaced with 16 O; (3) The deoxygenated water after the reaction is liquefied and separated from the carbon dioxide after the reaction to obtain isotopically labeled carbon dioxide.

7. The preparation method according to claim 6, characterized in that, In step (1), the molar ratio of deoxygenated water to carbon dioxide is (2-5):

1.

8. The preparation method according to claim 6, characterized in that, The vaporization temperature in step (1) is 100-300℃.

9. The preparation method according to claim 6, characterized in that, The volume hourly space velocity (VHSV) of the oxygen exchange reaction in step (2) is 5000-100000 h⁻¹ -1 .

10. The preparation method according to claim 6, characterized in that, The liquefaction temperature in step (3) is from -10°C to 20°C.

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