Apparatus system and method for preparing isotope-labeled carbon dioxide

Abstract

To provide an apparatus system and a method for preparing isotope-labeled carbon dioxide.SOLUTION: A preparation method includes vaporizing heavy oxygen water and then mixing the vaporized heavy oxygen water with carbon dioxide, catalyzing the mixture with a catalyst material, subjecting the heavy oxygen water and the carbon dioxide to oxygen substitution reaction, performing gas-liquid separation after reaction, and obtaining isotope-labeled carbon dioxide. An apparatus system has a simple structure, uses heavy oxygen water which is widely derived and inexpensive as an oxygen isotope source, achieves substitution oxygen-16 of general carbon dioxide with oxygen-18 of heavy oxygen water, obtains an oxygen-18 isotope-labeled carbon dioxide product, has a simple process, is green and has no contamination, has a high utilization rate of an oxygen isotope, has a mild separation purification condition, and has good economy benefits and prospective application.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to the technical field of carbon dioxide preparation, and in particular to an apparatus system and method for preparing isotope-labeled carbon dioxide. [Background technology]

[0002] In the context of "carbon peaking and carbon neutrality", the scientific research related to the capture, conversion and utilization of carbon dioxide has become a recognized research hotspot. In the carbon dioxide conversion reaction process, isotope tracing tests have 2 As an important means for investigating the conversion route and reaction mechanism, oxygen isotope-labeled carbon dioxide is the main material for isotope testing. However, the preparation and separation purification process of oxygen isotope-labeled carbon dioxide is complicated, and the price is very high, so the use of oxygen isotope-labeled carbon dioxide in related research fields is limited.

[0003] In CN114436260A, oxygen isotope-labeled oxalic acid is heated in a reaction vessel to decompose the oxalic acid and release oxygen isotope-labeled CO. 2 , CO and H 2 O was obtained, and CO was labeled with oxygen isotopes at different temperatures using a recovery bolt and a freezer. 2 , CO and H 2 An apparatus and method for preparing carbon monoxide and carbon dioxide labeled with oxygen isotopes by collecting O is disclosed. This method has a simple and efficient preparation process and product separation and purification process, and can obtain a carbon dioxide product with a high oxygen isotope utilization rate and an O-18 abundance of over 95%. However, this method uses oxygen isotope-labeled oxalic acid as an isotope source, which is expensive and requires harsh separation and purification conditions, requiring a freezing temperature of -100°C or lower.

[0004] Therefore, the development of a simple, green, efficient and low-cost apparatus system and method for preparing oxygen-18 isotope-labeled carbon dioxide has very important significance in meeting the needs for its use in related research fields.

Summary of the Invention

Problems to be Solved by the Invention

[0005] An object of the present invention is to provide an apparatus system and method for preparing isotope-labeled carbon dioxide, which has a wide source of raw materials, low cost, mild preparation conditions, a simple process, and good economic benefits and application prospects.

Means for Solving the Problems

[0006] To achieve the object of the present invention, the present invention has taken the following technical solutions.

[0007] In a first aspect, the present invention is an apparatus system for preparing isotope-labeled carbon dioxide, the apparatus system including a preparation unit, a heavy water raw material storage device, a carbon dioxide raw material storage device, a product storage device and a heavy water recovery storage device, the preparation unit including a heating vaporization device, an oxygen substitution reaction device provided with a catalyst material, and a gas-liquid separation device connected in sequence, the inlet of the heating vaporization device being connected to the heavy water raw material storage device and the carbon dioxide raw material storage device respectively, and providing an apparatus system in which 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 water recovery storage device.

[0008] The device system according to the present invention has a simple structure, uses heavy water with a wide origin and low cost as an oxygen isotope source, and realizes the substitution of oxygen-16 in common carbon dioxide with oxygen-18 in heavy water through an oxygen substitution action, obtaining an oxygen-18 isotope-labeled carbon dioxide product. The process is simple, green and pollution-free, with a high utilization rate of oxygen isotopes, mild separation and purification conditions, and good economic benefits and application prospects.

[0009] Preferably, the device system includes at least one preparation unit.

[0010] The device system according to the present invention can flexibly arrange the preparation units according to the purity requirements of the product, with convenient arrangement and the ability to meet the needs of different products.

[0011] Preferably, when the device system includes two or more preparation units, along the flow direction of substances in the device system, the inlets of the heating vaporization devices of the subsequent preparation units are respectively connected to the heavy water raw material storage device and the gas phase outlet of the gas-liquid separation device in the previous preparation unit.

[0012] Preferably, when the device system includes two or more preparation units, a heat exchange device is further provided between two adjacent preparation units. Along the flow direction of substances in the device system, the heat medium inlet of the heat exchange device is connected to the outlet of the oxygen substitution reactor of 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 of the previous preparation unit. The heat medium outlet of the heat exchange device is connected to the inlet of the gas-liquid separation device of the subsequent preparation unit. The cold medium outlet of the heat exchange device is connected to the inlet of the heating vaporization device of the subsequent preparation unit.

[0013] Preferably, the catalyst material is γ-Al 2 O 3 、CeO 2It contains any one or a combination of at least two of them, such as anatase titanium dioxide. A typical combination is that of γ-Al 2 O 3 and CeO 2 and the combination of CeO 2 and anatase titanium dioxide, the combination of γ-Al 2 O 3 and anatase titanium dioxide, or the combination of γ-Al 2 O 3 , CeO 2 and anatase titanium dioxide, but is not limited thereto.

[0014] As a second aspect, the present invention provides a method for preparing isotope-labeled carbon dioxide using the device system described in the first aspect.

[0015] Preferably, the preparation method includes Step (1) of vaporizing heavy oxygen water and then mixing it with carbon dioxide to obtain a mixed gas, Catalyzing the mixed gas obtained in step (1) with a catalyst material to cause an oxygen substitution reaction between heavy oxygen water and carbon dioxide, so that 16 O in carbon dioxide is replaced by 18 O in heavy oxygen water to generate isotope-labeled carbon dioxide, and 18 O in heavy oxygen water is replaced by 16 O in step (2), Step (3) of liquefying the heavy oxygen water after the reaction and separating it from the carbon dioxide after the reaction to obtain isotope-labeled carbon dioxide.

[0016] Preferably, the molar ratio of heavy oxygen water to carbon dioxide described in step (1) is (2 - 5):1. For example, it may 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 unlisted values within the numerical range are equally applicable.

[0017] Preferably, the temperature of vaporization described in step (1) is 100 to 300 °C. For example, it may 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 recited values, and other values not recited within the numerical range are equally applicable.

[0018] Preferably, the volumetric space velocity of the oxygen substitution reaction described in step (2) is 5000 to 100000 h -1 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 but is not limited to the recited values, and other values not recited within the numerical range are equally applicable.

[0019] Preferably, the temperature of liquefaction described in step (3) is -10 °C to 20 °C. For example, it may be -10 °C, -5 °C, 0 °C, 5 °C, 10 °C, 15 °C or 20 °C, but is not limited to the recited values, and other values not recited within the numerical range are equally applicable.

Advantages of the Invention

[0020] Compared with the prior art, the present invention has the following beneficial effects.

[0021] The device system according to the present invention has a simple structure, uses heavy oxygen water with a wide origin and low cost as an oxygen isotope source, and realizes the substitution of oxygen-16 in common carbon dioxide with oxygen-18 in heavy oxygen water through an oxygen substitution action, obtaining an oxygen-18 isotope-labeled carbon dioxide product. The process is simple, green and pollution-free, the utilization rate of oxygen isotopes is high, the separation and purification conditions are mild, and it has good economic benefits and application prospects.

Brief Description of the Drawings

[0022]

Figure 1

Embodiments for Carrying out the Invention

[0023] The following further describes the technical solution of the present invention according to specific embodiments. Those skilled in the art should understand that the above-described embodiments are only for helping to understand the present invention and should not be regarded as specifically limiting the present invention.

[0024] Example 1 This example provides a device system for preparing isotope-labeled carbon dioxide as shown in Figure 1. The device system includes 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.

[0025] The first-stage preparation unit includes a first-stage heating vaporization device 3, a first-stage oxygen substitution reaction device 4, and a first-stage gas-liquid separation device 6 connected in sequence.

[0026] The second-stage preparation unit includes a second-stage heating vaporization device 7, a second-stage oxygen substitution reaction device 8, and a second-stage gas-liquid separation device 10, and the second-stage heating vaporization device 7 and the second-stage oxygen substitution reaction device 8 are connected.

[0027] The three-stage modulation unit includes a three-stage heating vaporization device 11, a three-stage oxygen substitution reaction device 12, and a three-stage gas-liquid separation device 14, and the three-stage heating vaporization device 11 and the three-stage oxygen substitution reaction device 12 are connected.

[0028] In the first-stage oxygen substitution reaction device 4, the second-stage oxygen substitution reaction device 8, and the third-stage oxygen substitution reaction device 12, a catalyst material 5 which is γ-Al 2 O 3 is provided.

[0029] The heavy oxygen water raw material storage device 1 is connected to the first-stage heating vaporization device 3, the second-stage heating vaporization device 7, and the third-stage heating vaporization device 11 respectively.

[0030] The carbon dioxide raw material storage device 2 and the first-stage heating vaporization device 3 are connected.

[0031] The cold medium inlet of the heat exchanger 9 is connected to the gas phase outlet of the first-stage gas-liquid separation device 6. The heat medium inlet of the heat exchanger 9 is connected to the second-stage oxygen substitution reaction device 8. The heat medium outlet of the heat exchanger 9 is connected to the second-stage gas-liquid separation device 10. The cold medium outlet of the heat exchanger 9 is connected to the second-stage heating vaporization device 7.

[0032] The cold medium inlet of the heat exchanger 13 is connected to the gas phase outlet of the second-stage gas-liquid separation device 10. The heat medium inlet of the heat exchanger 13 is connected to the third-stage oxygen substitution reaction device 12. The heat medium outlet of the heat exchanger 13 is connected to the third-stage gas-liquid separation device 14. The cold medium outlet of the heat exchanger 13 is connected to the third-stage heating vaporization device 11.

[0033] The product storage device 15 is connected to the gas phase outlet of the third-stage gas-liquid separation device 14.

[0034] The heavy oxygen water recovery storage device 16 is connected to the liquid phase outlets of the first-stage gas-liquid separation device 6, the second-stage gas-liquid separation device 10, and the third-stage gas-liquid separation device 14 respectively.

[0035] Example 2 This embodiment provides an apparatus system for preparing isotope-labeled carbon dioxide. The apparatus system includes a first-stage preparation unit, a second-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 and storage device 16, and a heat exchange device 9.

[0036] The first-stage preparation unit includes a first-stage heating and vaporization device 3, a first-stage oxygen substitution reaction device 4, and a first-stage gas-liquid separation device 6, which are connected in sequence.

[0037] The second-stage preparation unit includes a second-stage heating and vaporization device 7, a second-stage oxygen substitution reaction device 8, and a second-stage gas-liquid separation device 10, and the second-stage heating and vaporization device 7 is connected to the second-stage oxygen substitution reaction device 8.

[0038] In the first-stage oxygen substitution reaction device 4 and the second-stage oxygen substitution reaction device 8, a catalyst material 5 which is γ-Al 2 O 3 is provided.

[0039] The heavy oxygen water raw material storage device 1 is connected to the first-stage heating and vaporization device 3 and the second-stage heating and vaporization device 7 respectively.

[0040] The carbon dioxide raw material storage device 2 and the first-stage heating and vaporization device 3 are connected.

[0041] The cold medium inlet of the heat exchange device 9 is connected to the gas phase outlet of the first-stage gas-liquid separation device 6. The heat medium inlet of the heat exchange device 9 is connected to the second-stage oxygen substitution reaction device 8. The heat medium outlet of the heat exchange device 9 is connected to the second-stage gas-liquid separation device 10. The cold medium outlet of the heat exchange device 9 is connected to the second-stage heating and vaporization device 7.

[0042] The product storage device 15 is connected to the gas phase outlet of the second-stage gas-liquid separation device 10.

[0043] The heavy oxygen water recovery and storage device 16 is connected to the liquid phase outlets of the first-stage gas-liquid separation device 6 and the second-stage gas-liquid separation device 10 respectively.

[0044] Usage Example 1 This usage example provides a method for preparing isotope-labeled carbon dioxide. The preparation method uses the device system according to Example 1 and includes the following steps.

[0045] (1) After introducing the heavy oxygen water (H 2 18 O, present in liquid phase) provided by the heavy oxygen water raw material storage device 1 into the one-stage heating vaporization device 3, the heavy oxygen water is vaporized into the gas phase, and carbon dioxide (CO 2 ) is provided by the carbon dioxide raw material storage device 2. The gaseous heavy oxygen water and carbon dioxide are mixed, and the molar ratio of heavy oxygen water to carbon dioxide is 3:1, and the temperature of the mixed gas at the outlet of the one-stage heating vaporization device 3 is 120 °C.

[0046] (2) The mixed gas H 2 18 O and CO 2 is introduced into the one-stage oxygen substitution reaction device 4 (the reaction temperature of the one-stage oxygen substitution reaction device 4 is 110 °C, and the volume space velocity is 10000 h -1 ), and under the action of the catalyst material γ-Al 2 O 3 , H 2 18 O is decomposed, and the CO 2 adsorbed on the material reacts with oxygen by substitution, and the 2 O in CO 16 is substituted by the 2 18 O in H 18 O to generate oxygen-18 isotope-labeled carbon dioxide (C 18 O 16 O, C 18 O 18 O), and the 2 18 O in H 18 O is substituted by 16 O to generate H 2 16 O.

[0047] (3) The gas after the oxygen substitution reaction is cooled by the gas-liquid separation device 6 (the cooling temperature is -3 °C), and the separated liquid-phase water (H 2 18 O and H 216 O) is introduced into the oxygen-18 water recovery and storage device 16, and the separated gaseous carbon dioxide (C 16 O 16 O, C 18 O 16 O, C 18 O 18 O) is heated to 80°C in the heat exchanger 9.

[0048] (4) The gaseous carbon dioxide (C 16 O 16 O, C 18 O 16 O, C 18 O 18 O) and the oxygen-18 water further pass through the two-stage preparation unit and the three-stage preparation unit in sequence, and perform the same vaporization, oxygen substitution reaction, and gas-liquid separation processes as in steps (1) to (3), and the obtained isotope-labeled carbon dioxide product is introduced into the product storage device 15.

[0049] In this example, the proportion of C 2 in CO at the gas phase outlet of the one-stage gas-liquid separator 6 18 O 18 O is 52%, and the proportion of C 2 in CO at the gas phase outlet of the two-stage gas-liquid separator 10 18 O 18 O is 84%, and the proportion of C 2 in CO at the gas phase outlet of the three-stage gas-liquid separator 14 18 O 18 O is 98%.

[0050] Usage Example 2 This usage example provides a method for preparing isotope-labeled carbon dioxide. The preparation method uses the device system according to Example 1 and includes the following steps.

[0051] (1) The oxygen-18 water (H 2 18 O, present in liquid phase) provided by the oxygen-18 water raw material storage device 1 is introduced into the one-stage heating vaporizer 3, and then the oxygen-18 water is liquefied into gas phase, and carbon dioxide (CO 2(1) is provided to mix gaseous heavy oxygen water and carbon dioxide, with the molar ratio of heavy oxygen water to carbon dioxide being 2:1, and the temperature of the mixed gas at the outlet of the single-stage heating vaporizer 3 being 100°C.

[0052] (2) The mixed gas H 2 18 O and CO 2 is introduced into the single-stage oxygen substitution reactor 4 (the reaction temperature of the single-stage oxygen substitution reactor 4 is 110°C, and the volume space velocity is 5000 h -1 ), and under the action of the catalyst material γ-Al 2 O 3 , H 2 18 O is decomposed, and the CO 2 adsorbed on the material undergoes an oxygen substitution reaction with oxygen, and the 2 O in CO 16 is substituted by the 2 18 O in H 18 O to generate oxygen-18 isotope-labeled carbon dioxide (C 18 O 16 O, C 18 O 18 O), and the 2 18 O in H 18 O is substituted by 16 O to generate H 2 16 O.

[0053] (3) The gas after the oxygen substitution reaction is cooled by the gas-liquid separation device 6 (the cooling temperature is -10°C), and the separated liquid-phase water (H 2 18 O and H 2 16 O) is introduced into the heavy oxygen water recovery and storage device 16, and the separated gaseous carbon dioxide (C 16 O 16 O, C 18 O 16 O, C 18 O 18 O) is heated to 80°C in the heat exchanger 9.

[0054] (4) The gaseous carbon dioxide (C 16 O 16 O, C18 O 16 O, C 18 O 18 O) and heavy oxygen water further passed through a two-stage preparation unit and a three-stage preparation unit in sequence, and underwent a vaporization, oxygen substitution reaction, and gas-liquid separation process similar to those in steps (1) to (3), and the obtained isotope-labeled carbon dioxide product was introduced into the product storage device 15.

[0055] In this example, the CO at the gas phase outlet of the first-stage gas-liquid separator 6 2 C in 18 O 18 The proportion of O is 45%, and the CO at the gas phase outlet of the second-stage gas-liquid separator 10 2 C in 18 O 18 The proportion of O is 72%, and the CO at the gas phase outlet of the third-stage gas-liquid separator 14 2 C in 18 O 18 The proportion of O is 88%.

[0056] Usage Example 3 This usage example provides a method for preparing isotope-labeled carbon dioxide. The preparation method uses the device system according to Example 1 and includes the following steps.

[0057] (1) The heavy oxygen water (H 2 18 O, present in liquid phase) provided by the heavy oxygen water raw material storage device 1 was introduced into the first-stage heating vaporization device 3, and then the heavy oxygen water was vaporized into the gas phase. Carbon dioxide (CO 2 ) was provided by the carbon dioxide raw material storage device 2, and the gaseous heavy oxygen water and carbon dioxide were mixed. The molar ratio of heavy oxygen water to carbon dioxide was 5:1, and the temperature of the mixed gas at the outlet of the first-stage heating vaporization device 3 was 300 °C.

[0058] (2) The mixed gas H 2 18 O and CO 2 entered the first-stage oxygen substitution reactor 4 (the reaction temperature of the first-stage oxygen substitution reactor 4 was 110 °C, and the volume space velocity was 100000 h -1 ), and the catalyst material γ-Al 2 O 3Under the action of H 2 18 O is decomposed, and the CO adsorbed on the material 2 reacts with oxygen in a substitution reaction, and the 2 O in CO 16 is replaced by H 2 18 O in H 18 O, generating oxygen-18 isotope-labeled carbon dioxide (C 18 O 16 O, C 18 O 18 O), and the 2 18 O in H 18 O is replaced by 16 O, generating H 2 16 O.

[0059] (3) The gas after the oxygen substitution reaction is cooled by the gas-liquid separation device 6 (the cooling temperature is 20 °C), and the separated liquid-phase water (H 2 18 O and H 2 16 O) enters the heavy oxygen water recovery and storage device 16, and the separated gaseous carbon dioxide (C 16 O 16 O, C 18 O 16 O, C 18 O 18 O) is heated to 80 °C in the heat exchange device 9.

[0060] (4) The gaseous carbon dioxide (C 16 O 16 O, C 18 O 16 O, C 18 O 18 O) after the first-stage oxygen substitution reaction and the heavy oxygen water further pass through the second-stage preparation unit and the third-stage preparation unit in sequence, and perform the same vaporization, oxygen substitution reaction, and gas-liquid separation processes as in steps (1) to (3), and the obtained isotope-labeled carbon dioxide product enters the product storage device 15.

[0061] In this example, the C in the CO at the gas-phase outlet of the first-stage gas-liquid separation device 6 2 18 O 18 ​The proportion of O is 64%, and the CO at the gas-phase outlet of the two-stage gas-liquid separator 10 2 in the C 18 O 18 The proportion of O is 87%, and the CO at the gas-phase outlet of the three-stage gas-liquid separator 14 2 in the C 18 O 18 The proportion of O is 99%.

[0062] Usage Example 4 This usage example provides a method for preparing isotope-labeled carbon dioxide. The preparation method uses the device system according to Example 1. Compared with Usage Example 1, it is the same as Usage Example 1 except that the molar ratios of heavy oxygen water to carbon dioxide in the single-stage heating vaporizer 3, the two-stage heating vaporizer 7, and the three-stage heating vaporizer are 2:1, 3:1, and 4:1 respectively.

[0063] In this usage example, the CO at the gas-phase outlet of the single-stage gas-liquid separator 6 2 in the C 18 O 18 The proportion of O is 40%, and the CO at the gas-phase outlet of the two-stage gas-liquid separator 10 2 in the C 18 O 18 The proportion of O is 75%, and the CO at the gas-phase outlet of the three-stage gas-liquid separator 14 2 in the C 18 O 18 The proportion of O is 96%.

[0064] Usage Example 5 This usage example provides a method for preparing isotope-labeled carbon dioxide. The preparation method uses the device system according to Example 1. Compared with Usage Example 1, the catalyst materials in the single-stage oxygen substitution reactor 4, the two-stage oxygen substitution reactor 8, and the three-stage oxygen substitution reactor 12 are replaced with an equal amount of CeO 2 therein.

[0065] In this usage example, the CO at the gas-phase outlet of the single-stage gas-liquid separator 6 2 in the C 18 O 18 The proportion of O is 50%, and the CO at the gas-phase outlet of the two-stage gas-liquid separator 10 2 in the C 18 O 18The proportion of O is 82%, and the CO at the gas-phase outlet of the three-stage gas-liquid separation device 14 2 C in 18 O 18 The proportion of O is 95%.

[0066] Usage Example 6 This usage example provides a method for preparing isotope-labeled carbon dioxide. The preparation method uses the device system according to Example 1. Compared with Usage Example 1, the catalyst materials in the first-stage oxygen substitution reactor 4, the second-stage oxygen substitution reactor 8, and the third-stage oxygen substitution reactor 12 are replaced with anatase-type titanium dioxide in equal amounts.

[0067] In this usage example, the CO at the gas-phase outlet of the first-stage gas-liquid separation device 6 2 C in 18 O 18 The proportion of O is 48%, and the CO at the gas-phase outlet of the second-stage gas-liquid separation device 10 2 C in 18 O 18 The proportion of O is 78%, and the CO at the gas-phase outlet of the third-stage gas-liquid separation device 14 2 C in 18 O 18 The proportion of O is 90%.

[0068] Comparative Usage Example 1 This comparative usage example provides a method for preparing isotope-labeled carbon dioxide. The preparation method uses the device system according to Example 1. Compared with Usage Example 1, no catalyst material is provided in the first-stage oxygen substitution reactor 4, the second-stage oxygen substitution reactor 8, and the third-stage oxygen substitution reactor 12.

[0069] In this comparative usage example, there is no catalyst material in the oxygen substitution reactor, and heavy water and CO 2 cannot undergo an oxygen substitution reaction, and the oxygen in CO 2 is not replaced by O-18.

Table 1

[0070] As can be seen from Table 1, the apparatus system and method according to the present invention can realize the preparation of isotope-labeled carbon dioxide by performing oxygen substitution with heavy oxygen water. After two-stage oxygen substitution, the concentration of C 18 O 2 can reach 72% or more. After three-stage oxygen substitution, its concentration can be improved to 88% or more. The reaction efficiency is high, the preparation purity is high, the utilization rate of heavy oxygen water as the reaction raw material is high, and the heavy oxygen water after the reaction can be collected in the storage device and reused.

[0071] In short, the apparatus system according to the present invention has a simple structure, uses heavy oxygen water, which is widely sourced and inexpensive, as an oxygen isotope source, and realizes the substitution of oxygen-16 in ordinary carbon dioxide with oxygen-18 in heavy oxygen water through the oxygen substitution effect to obtain an oxygen-18 isotope-labeled carbon dioxide product. The process is simple, green, pollution-free, has a high utilization rate of oxygen isotopes, mild separation and purification conditions, and has good economic benefits and application prospects.

[0072] The applicant hereby declares that the above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention are all within the protection scope and disclosure scope of the present invention.

Explanation of Reference Numerals

[0073] 1: Heavy oxygen water raw material storage device; 2: Carbon dioxide raw material storage device; 3: First-stage heating vaporization device; 4: First-stage oxygen substitution reaction device; 5: Catalyst material; 6: First-stage gas-liquid separation device; 7: Second-stage heating vaporization device; 8: Second-stage oxygen substitution reaction device; 9: Heat exchange device; 10: Second-stage gas-liquid separation device; 11: Third-stage heating vaporization device; 12: Third-stage oxygen substitution reaction device; 13: Heat exchange device; 14: Third-stage gas-liquid separation device; 15: Product storage device; 16: Heavy oxygen water recovery storage device.

Claims

1. 1. An apparatus system for preparing isotope-labeled carbon dioxide, comprising: The equipment 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 storage device; The preparation unit includes a heating vaporizer, an oxygen substitution reaction device provided with a catalytic material, and a gas-liquid separator, which are connected in series; The inlets of the heating vaporizer are respectively connected to a heavy oxygen water source storage device and a carbon dioxide source storage device; The gas-liquid separator has a gas-phase outlet connected to a product storage device, and a liquid-phase outlet connected to a heavy oxygen water recovery and storage device.

2. The equipment system of claim 1 , wherein the equipment system comprises at least one preparation unit.

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

4. When the equipment system includes two or more preparation units, a heat exchange device is further provided between two adjacent preparation units, According to the flow direction of the material in the equipment system, the heat medium inlet of the heat exchanger is connected to the outlet of the oxygen substitution reaction device of the subsequent preparation unit; The refrigerant inlet of the heat exchanger is connected to the gas phase outlet of the gas-liquid separator of the previous preparation unit; The heat medium outlet of the heat exchanger is connected to the inlet of a gas-liquid separator of a subsequent preparation unit; 3. The system according to claim 2, characterized in that the refrigerant outlet of the heat exchanger is connected to the inlet of a heating vaporizer of a subsequent preparation unit.

5. The catalytic material is γ-Al ２ O ３ , CeO ２ or anatase type titanium dioxide, or a combination of at least two of them.

6. 1. A method for preparing isotope-labeled carbon dioxide, comprising the steps of: The preparation method is characterized in that the preparation method uses an apparatus system according to any one of claims 1 to 5.

7. The preparation method comprises the steps of: A step (1) of vaporizing heavy oxygen water and then mixing it with carbon dioxide to obtain a mixed gas; The mixed gas obtained in step (1) is catalyzed with a catalyst material, and the deuterium oxide and carbon dioxide are subjected to an oxygen substitution reaction, and the deuterium oxide in the carbon dioxide is １６ O in deoxygenated water １８ O is substituted to generate isotope-labeled carbon dioxide, １８ O １６ Step (2) of replacing with O; The method according to claim 6, further comprising the step (3) of liquefying the reacted deuterium oxide water and separating the reacted carbon dioxide from the deuterium oxide water into gas and liquid to obtain isotope-labeled carbon dioxide.

8. 8. The method according to claim 7, wherein the molar ratio of deuterium oxide to carbon dioxide in step (1) is (2-5):

1.

9. The preparation method according to claim 7, characterized in that the temperature of vaporization in step (1) is 100-300°C.

10. The volumetric space velocity of the oxygen substitution reaction described in step (2) is 5,000 to 100,000 h －１ and The preparation method according to claim 7, characterized in that the temperature of the liquefaction according to step (3) is preferably between -10°C and 20°C.

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