A sort of 13 CO2 production device and production method

Abstract

The present invention relates to the technical field of isotope product processing, and specifically discloses a CO2 production device and a production method with high product purity and yield and low production cost. The device includes a catalytic oxidation reactor, a nitrogen gas cylinder, a CO gas cylinder, and an oxygen gas cylinder connected to the input end of the catalytic oxidation reactor, a CO2 crude product cold trap and a CO2 product cold trap selectively connected to the output end of the catalytic oxidation reactor, the CO2 crude product cold trap and the CO2 product cold trap are combined and then selectively connected to a CO2 crude product cylinder and a CO2 product cylinder, and the output end of the catalytic oxidation reactor is connected to an analysis device. The method includes: catalytic oxidation reaction of a catalyst, oxygen and CO gas in the catalytic oxidation reactor to obtain a CO2 crude product; collecting the CO2 crude product and sampling and analyzing whether the product is qualified; cooling the product to convert CO2 into a solid, evacuating and boosting pressure to remove impurities of the product and bottling it. 13 A nitrogen gas cylinder, a CO gas cylinder, and an oxygen gas cylinder connected to the input end of the catalytic oxidation reactor 13 A CO2 crude product cold trap and 13 A CO2 product cold trap 13 13 The CO2 crude product cold trap and 13 The CO2 product cold trap are combined and then selectively connected to 13 A CO2 crude product cylinder and 13 A CO2 product cylinder, and the output end of the catalytic oxidation reactor is connected to an analysis device. 13 Catalytic oxidation reaction of a catalyst, oxygen and CO gas in the catalytic oxidation reactor to obtain 13 A CO2 crude product; collecting 13 The CO2 crude product and sampling and analyzing whether the product is qualified; cooling the product to make 13 CO2 turn into a solid, evacuating and boosting pressure to remove impurities of the product and bottling it.​

Description

Technical Field

[0001] The present invention relates to the technical field of isotope product processing, and in particular to a 13 CO2 production device and production method. Background Art

[0002] In nature, carbon has 12 C and 13 C has two stable isotopes, which have the same number of protons but different numbers of neutrons, and their natural abundances are 98.89% and 1.11% respectively. As an important raw material for the synthesis of labeled drugs, at present, 13 The main production method of CO is CO cryogenic distillation. 12 CO and 13 The difference in CO volatility is achieved by using cryogenic distillation. 12 CO and 13 CO isotope separation to produce 13 CO, taking into account 13 CO is a toxic gas that is difficult to store and transport. The most effective method is to 13 CO gas is used as the starting material to produce 13 CO2, 13 CO2 is less toxic, can be filled in large quantities in cylinders of the same volume, and is easy to store and transport. 13 CO2 can be used as raw material to produce many downstream 13 C-labeled compounds, such as 13 C-pyruvic acid, 13 C-caprylic acid, 13 C-sodium bicarbonate, 13 C-acetic acid, etc., and ultimately used in medicine, agriculture, scientific research and other fields, and 13 CO2 has a high selling price and high added value, which can create good economic benefits.

[0003] because 12 CO and 13 The difference in CO volatility is small, and low-temperature distillation separation 13 CO isotopes require thousands of theoretical plates, and the required cryogenic distillation tower is more than 100 meters high. The engineering difficulty and equipment investment are large, and it is also a high energy consumption process. 13 CO raw materials are expensive. Therefore, it is required to 13 In the process of CO2, we should try our best to increase 13 The conversion rate of CO raw materials and the yield of products can be improved to reduce production costs. 13 The production scale of CO2 is generally very small, ranging from tens of grams to tens of kilograms, and industrial carbon dioxide production equipment is not applicable. Table 1 shows the boiling points of different fractions when cryogenic distillation is used.

[0004] Table 1 Boiling points of raw materials, products and impurity gases

[0005] Compound Structural formula Boiling point / ℃ oxygen <![CDATA[O2]]> -183 Nitrogen <![CDATA[N2]]> -195.8 <![CDATA[ 13 C-Carbon Monoxide]]> <![CDATA[ 13 CO]]> -191.5 <![CDATA[ 13 C-Carbon Dioxide]]> <![CDATA[ 13 CO2]]> -78.5℃(sublimation)

[0006] on the other hand, 13 After catalytic oxidation of CO, the 13 The crude CO2 will inevitably contain 13 Due to the small scale of production, the amount of gas impurities such as CO and O2 is only tens of grams to tens of kilograms. The conventional distillation and adsorption methods will cause the loss of some products during the operation, resulting in a significant reduction in yield. 13 The purity requirement of CO2 products needs to be greater than 99.8%, and the main packaging method is filling in steel cylinders. Therefore, it is necessary to design an effective purification method to remove 13 Impurities in CO2 are removed to ensure the yield while improving the purity of the product, and the filling method is studied to ensure that qualified products are obtained.

[0007] At present, most of the CO2 production methods in the field are industrial catalytic oxidation of carbon monoxide to produce ordinary carbon dioxide. Such methods are too large in scale and are not suitable for small-scale production of isotope products. The existing carbon dioxide purification methods are mainly adsorption and distillation methods. When the amount of raw materials is only a few dozen grams, the product loss is large, resulting in a low purification yield. The current CO2 production method is difficult to meet 13 CO2 production 13 The demand for high conversion rate of C element and high yield of reaction and purification. Summary of the invention

[0008] Based on this, it is necessary to provide a product with high purity and yield and low production cost to address the above shortcomings. 13 CO2 production device and production method.

[0009] A sort of 13 The CO2 production device comprises a catalytic oxidation reactor for loading a catalyst and providing a catalytic oxidation reaction site, a nitrogen cylinder connected to an input end of the catalytic oxidation reactor, 13 A CO gas cylinder and an oxygen cylinder are arranged at the output end of the catalytic oxidation reactor and one of them is connected to the output end of the catalytic oxidation reactor. 13 CO2 crude cold trap and 13 CO2 product cold trap, and for holding 13 CO2 crude 13 CO2 crude product cylinders and for 13 CO2 products 13 CO2 product cylinders, 13 The output end of the CO2 crude product cold trap is13 The output end of the CO2 product cold trap merges and flows through the merging pipe with 13 CO2 crude cylinders and 13 The output end of the catalytic oxidation reactor is also connected to the analysis equipment; the output end of the confluence pipe is also connected to the analysis equipment, the vacuum device and the venting device; the catalytic oxidation reactor is provided with a first heating unit, 13 The CO2 crude product cold trap is equipped with a second heating unit and a first liquid nitrogen cooling unit. 13 The CO2 product cold trap is provided with a third heating unit and a second liquid nitrogen cooling unit.

[0010] In one embodiment, the input end of the catalytic oxidation reactor is connected to a first main pipe, and the end of the first main pipe away from the catalytic oxidation reactor is respectively connected to a first branch pipe, a second branch pipe and a third branch pipe, the first branch pipe is connected to a nitrogen cylinder, the second branch pipe is connected to a nitrogen cylinder, 13 The output end of the catalytic oxidation reactor is connected to the second main pipe, and the end of the second main pipe away from the catalytic oxidation reactor is respectively connected to the fourth branch pipe, the fifth branch pipe and the sixth branch pipe, the fourth branch pipe is used to be connected to the detection port of the analysis equipment, the fifth branch pipe is connected to the detection port of the analysis equipment, and the fifth branch pipe is connected to the detection port of the analysis equipment. 13 The CO2 crude product cold trap is connected to the sixth branch pipe. 13 The CO2 product cold trap is connected; the input end of the confluence pipe is connected to 13 CO2 crude product cold trap connection 13 The crude product output pipe of CO2 crude product and 13 CO2 product cold trap connection 13 The CO2 product output pipe is connected to the output end of the confluence pipe through the crude product input pipe. 13 The crude CO2 cylinder is connected to the product outlet pipe. 13 The output end of the confluence pipe is also connected to the seventh branch pipe connected to the detection port of the analysis equipment, the eighth branch pipe connected to the vacuum device and the ninth branch pipe connected to the venting device; the catalytic oxidation reactor, 13 CO2 crude cold trap, 13 The CO2 product cold trap and pipelines are made of stainless steel.

[0011] In one embodiment, the first branch pipe is provided with a nitrogen flow meter and a nitrogen inlet valve, and the second branch pipe is provided with 13 CO gas flow meter and 13a CO inlet valve, an oxygen flowmeter and an oxygen inlet valve are arranged on the third branch pipe, an inlet valve of a catalytic oxidation reactor is arranged on the first main pipe, an outlet valve of a catalytic oxidation reactor, a dust collector and a filter are arranged on the second main pipe, a first sampling valve is arranged on the fourth branch pipe, a crude product cold trap inlet valve is arranged on the fifth branch pipe, a product cold trap inlet valve is arranged on the sixth branch pipe, a crude product cold trap outlet valve is arranged on the crude product output pipe, a product cold trap outlet valve is arranged on the product output pipe, a crude product cylinder inlet valve is arranged on the crude product input pipe, a product cylinder inlet valve is arranged on the product input pipe, a second sampling valve is arranged on the seventh branch pipe, a vacuum valve is arranged on the eighth branch pipe, and a vent valve is arranged on the ninth branch pipe; 13 The CO2 production device also includes a control unit for controlling the on and off of each valve.

[0012] In one embodiment, the catalytic oxidation reactor, 13 CO2 crude cold trap, 13 The CO2 product cold trap and each pipeline are made of stainless steel; the diameter of the catalytic oxidation reactor is 10mm to 50mm; the length of the catalytic oxidation reactor is 100mm to 500mm; the filtration accuracy of the filter is 0.003μm to 0.5μm.

[0013] The present invention also discloses a 13 CO2 production method, using the above 13 The CO2 production device comprises the following steps:

[0014] S1: Load the catalyst into the catalytic oxidation reactor and introduce oxygen and 13 CO gas is subjected to catalytic oxidation reaction to obtain 13 CO2 crude product;

[0015] S2: Adoption 13 CO2 crude product cold trap collection 13 CO2 crude product is sampled and analyzed, and the content of 13 C abundance and 13 CO conversion rate and judging whether the product is qualified;

[0016] S3: Adoption 13 CO2 product cold trap collects qualified products and cools the products down. 13 CO2 turns into solid 13 The gas in the CO2 product cold trap is evacuated and pressurized to remove 13 CO2 product cold trap contains impurities and the impurity-free product is loaded into 13 CO2 product cylinders.

[0017] In one embodiment, in step S1, oxygen and 13 Before CO gas is introduced, it also includes:

[0018] S01: Under heating conditions, the nitrogen inlet valve, the catalytic oxidation reactor inlet valve, the catalytic oxidation reactor outlet valve, the crude product cold trap inlet valve, the product cold trap inlet valve, the crude product cold trap outlet valve, the product cold trap outlet valve and the vent valve are opened in sequence, and high-purity nitrogen is passed into the catalytic oxidation reactor to purge and remove water, and the output gas of the ninth branch pipe is passed into the trace water analyzer for detection until the gas moisture is qualified, and then the nitrogen inlet valve and the vent valve are closed;

[0019] S02: Open the vacuum valve and evacuate the catalytic oxidation reactor.

[0020] In one embodiment, step S2 comprises:

[0021] S21: Cool down by introducing liquid nitrogen 13 CO2 crude cold trap and 13 CO2 product cold trap, open the catalytic oxidation reactor outlet valve, 13 The crude CO2 enters the dust collector and filter 13 CO2 crude cold trap;

[0022] S22: After passing through the first sampling valve at the outlet of the catalytic oxidation reactor 13 CO2 crude product in cold trap 13 CO2 crude product sampling and analysis 13 CO conversion rate and product 13 When the C abundance is qualified, open the product cold trap air inlet valve and pass the qualified product into 13 CO2 product cold trap.

[0023] In one embodiment, step S3 comprises:

[0024] S31: After the qualified products are collected, close the oxygen inlet valve, 13 The CO inlet valve and the catalytic oxidation reactor outlet valve are opened, and the product cold trap outlet valve is opened. 13 Detection and analysis of gas in CO2 product cold trap 13 CO2 purity, 13 CO and O2 content;

[0025] S32: Yes 13 The CO2 product cold trap is cooled to -90℃~-130℃, and the vacuum valve is opened to 13 The CO2 product cold trap is evacuated to -0.095MPa~-0.098MPa, light impurities are removed, and the vacuum valve is closed; liquid nitrogen is stopped, and the 13 The CO2 product cold trap is pressurized to 0.05MPa~0.2MPa, and the gas is tested;

[0026] S33: Repeat step S32 until the product purity reaches the required level, and then close the product cold trap outlet valve.

[0027] In one embodiment, step S3 further includes:

[0028] S34: Open the vacuum valve and the gas inlet valve of the product cylinder, evacuate the product cylinder until the absolute pressure reaches below 10Pa, close the vacuum valve, and 13 The CO2 product cold trap is pressurized to 0.2MPa~7MPa, and the product cold trap outlet valve and product cylinder inlet valve are opened. 13 The CO2 product is filled into the product cylinder;

[0029] S35: 13 The CO2 crude product cold trap is pressurized to 0.2MPa~7MPa, and the crude product cold trap outlet valve and crude product cylinder inlet valve are opened. 13 The crude CO2 is charged into the crude product cylinder.

[0030] In one embodiment, the input to the catalytic oxidation reactor 13 The flow rate of CO is 0.01kg / h~2kg / h; the oxygen and 13 The volume ratio of CO is 1.01-1.2; the catalyst in the catalytic oxidation reactor uses one or more of Pt, Pd, Cu, Co, and Ir as active components, and uses one or more of aluminum oxide, titanium oxide, zinc oxide, and cerium oxide as carriers.

[0031] Implementation of the present invention 13 The CO2 production device and production method can at least achieve the following beneficial effects:

[0032] 1) Suitable for small batch production of stable isotopes, with low equipment investment, simple operation, high product yield, low cost and good economy;

[0033] 2) Production 13 CO2 purity is greater than 99.8%, 13 The C isotope abundance is greater than 98%, and the product purity and abundance meet the application requirements;

[0034] 3) Production 13 CO2, 13 CO conversion rate is greater than 95%, making full use of expensive 13 CO raw material, high product yield and low cost;

[0035] 4) The production and purification methods used effectively remove 13 Light components such as CO, O2, and N2 have less product loss during purification, effectively reducing production costs;

[0036] 5) CO2 is turned into solid under low temperature conditions and then removed by vacuum. 13 Light components such as CO, O2, and N2 can reduce the total content of the above impurities to less than 0.2%;

[0037] 6) Nitrogen purging is performed before the reaction to remove moisture from the reaction system, so that the water content in the product is less than 10 ppm, thereby ensuring the quality of the product and preventing water from freezing in the pipeline and clogging the pipeline;

[0038] 7) It avoids the high energy consumption of traditional distillation methods and reduces the amount of cold and heat consumed in the production process;

[0039] 8) The device is suitable for the production method of the present invention, and the purity is greater than 99.8%. 13 C isotope abundance greater than 98% 13 CO2. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 In one embodiment of the present invention 13 Schematic diagram of the structure of the CO2 production device;

[0041] Figure 2 In one embodiment of the present invention 13 Flowchart of the CO2 production method. DETAILED DESCRIPTION

[0042] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific embodiments of the present invention are described in detail below in conjunction with the accompanying drawings. In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without violating the connotation of the present invention, so the present invention is not limited by the specific embodiments disclosed below.

[0043] The present invention is aimed at the current 13 In the CO2 production process, due to the use of 13 When CO is used as the reaction raw material, the raw material is expensive and the yield is insufficient, resulting in low product yield and high production cost. 13 After catalytic oxidation of CO, 13 The crude CO2 will inevitably contain 13 Due to the small scale of production, the amount of gas impurities such as CO and O2 is only tens of grams to tens of kilograms. The conventional distillation and adsorption methods will cause the loss of part of the product during the operation, resulting in a further reduction in the yield. 13 CO as a reaction raw material, suitable for small-scale 13 CO2 production 13CO2 production device and production method, the production device and production method are 13 CO is used as raw material to produce 13 CO2, and purify it to remove 13 After purification, the CO purity of CO2, such as CO, O2, N2 and other gas impurities, is above 99.8%, which meets the needs of users and is suitable for small-batch production of stable isotopes with high yield, low equipment investment, simple operation and low production cost.

[0044] For details, please refer to Figure 1 , the present invention 13 The CO2 production device comprises a catalytic oxidation reactor R1 for loading catalyst and providing a catalytic oxidation reaction site, a nitrogen cylinder C1 connected to the input end of the catalytic oxidation reactor R1, 13 The CO gas cylinder C2 and the oxygen cylinder C3 are arranged at the output end of the catalytic oxidation reactor R1 and are connected to the output end of the catalytic oxidation reactor R1. 13 CO2 crude cold trap L1 and 13 CO2 product cold trap L2, and for holding 13 CO2 crude 13 CO2 crude product cylinder C4 and used for 13 CO2 products 13 CO2 product cylinder C5, 13 The output end of CO2 crude product cold trap L1 is 13 The output end of CO2 product cold trap L2 merges and flows through the merging pipe with 13 CO2 crude product cylinder C4 and 13 The CO2 product cylinder C5 is connected to one of them, and the output end of the catalytic oxidation reactor R1 is also connected to an analysis device; the output end of the confluence pipe is also connected to the analysis device, the vacuum device and the venting device. In this embodiment, the diameter of the catalytic oxidation reactor R1 is 10mm to 50mm; the length of the catalytic oxidation reactor R1 is 100mm to 500mm. Preferably, the diameter of the catalytic oxidation reactor R1 is 20mm to 40mm, and the length of the catalytic oxidation reactor R1 is 200mm to 400mm. The catalyst for the catalytic oxidation reaction contained in the catalytic oxidation reactor R1 has one or more of Pt, Pd, Cu, Co, and Ir as active components, and one or more of aluminum oxide, titanium oxide, zinc oxide and cerium oxide as carriers. 13 The CO gas cylinder C2 and the oxygen cylinder C3 are used to provide the raw gas for the catalytic oxidation reaction to the catalytic oxidation reactor R1, and the nitrogen cylinder C1 is used to provide nitrogen to the catalytic oxidation reactor R1 before the catalytic oxidation reaction. The nitrogen is used to purge the inside of the catalytic oxidation reactor R1 to remove the air and moisture in the catalytic oxidation reactor R1, so as to avoid the residual air and water in the catalytic oxidation reactor R1 from13 The catalytic oxidation reaction of CO gas is disturbed.

[0045] A first heating unit is provided in the catalytic oxidation reactor R1. 13 The CO2 crude product cold trap L1 is provided with a second heating unit and a first liquid nitrogen cooling unit. 13 The CO2 product cold trap L2 is provided with a third heating unit and a second liquid nitrogen cooling unit. In this embodiment, a first heating unit is provided in the catalytic oxidation reactor R1. 13 The CO gas and oxygen undergo catalytic oxidation under the action of the catalyst, providing a heat source; 13 CO2 crude cold trap L1 and 13 The heating unit and liquid nitrogen cooling unit in the CO2 product cold trap L2 are 13 The phase change of each component in the CO2 crude product provides conditions. In this embodiment, the catalytic oxidation reactor R1 provides 13 The reaction and generation site of CO2, 13 The purification of crude CO2 product is carried out in 13 CO2 crude cold trap L1 and 13 In addition, in this embodiment, the catalytic oxidation reactor R1, 13 CO2 crude cold trap L1, 13 The CO2 product cold trap L2 is made of stainless steel to ensure 13 Safety during CO2 production.

[0046] Furthermore, the input end of the catalytic oxidation reactor R1 is connected to a first main pipe, and the end of the first main pipe away from the catalytic oxidation reactor R1 is respectively connected to a first branch pipe, a second branch pipe and a third branch pipe, the first branch pipe is connected to the nitrogen cylinder C1, the second branch pipe is connected to the nitrogen cylinder C2, and the third branch pipe is connected to the nitrogen cylinder C3. 13 The third branch pipe is connected to the CO gas cylinder C2, and the third branch pipe is connected to the oxygen cylinder C3; the output end of the catalytic oxidation reactor R1 is connected to the second main pipe, and the end of the second main pipe away from the catalytic oxidation reactor R1 is respectively connected to the fourth branch pipe, the fifth branch pipe and the sixth branch pipe, the fourth branch pipe is used to connect to the detection port of the analysis equipment, and the fifth branch pipe is connected to the detection port of the analysis equipment. 13 The CO2 crude product cold trap L1 is connected to the sixth branch pipe. 13 The CO2 product cold trap L2 is connected; the input end of the confluence pipe is connected to 13 CO2 crude product cold trap L1 access 13 The crude product output pipe of CO2 crude product and 13 CO2 product cold trap L2 connection 13 The CO2 product output pipe and the output end of the confluence pipe are connected to the crude product input pipe through 13 The crude CO2 cylinder C4 is connected to the product outlet pipe. 13The output end of the confluence pipe is also connected to the seventh branch pipe connected to the detection port of the analysis equipment, the eighth branch pipe connected to the vacuum device, and the ninth branch pipe connected to the venting device. In this embodiment, the material of each pipeline is stainless steel to ensure the safety of gas transportation and avoid safety accidents caused by pipeline damage.

[0047] In this embodiment, the first branch pipe is provided with a nitrogen flow meter FC1 and a nitrogen inlet valve V1, and the second branch pipe is provided with a 13 CO gas flow meter FC2 and 13 The third branch pipe is provided with an oxygen flowmeter FC3 and an oxygen intake valve V3, the first main pipe is provided with a catalytic oxidation reactor inlet valve V4, the second main pipe is provided with a catalytic oxidation reactor outlet valve V5, a dust collector B1 and a filter F1. The filtration accuracy of the filter F1 is 0.003μm to 0.5μm to remove the generated 13 Impurities in the crude CO2 product are prevented from being carried in the gas by catalyst or particles peeled off from the inner surface of the catalytic oxidation reactor R1. The fourth branch pipe is provided with a first sampling valve V6, the fifth branch pipe is provided with a crude product cold trap air inlet valve V7, the sixth branch pipe is provided with a product cold trap air inlet valve V8, the crude product output pipe is provided with a crude product cold trap air outlet valve V9, the product output pipe is provided with a product cold trap air outlet valve V10, the crude product input pipe is provided with a crude product cylinder air inlet valve V14, the product input pipe is provided with a product cylinder air inlet valve V15, the seventh branch pipe is provided with a second sampling valve V11, the eighth branch pipe is provided with a vacuum valve V12, and the ninth branch pipe is provided with a vent valve V13; 13 The CO2 production device also includes a control unit for controlling the on and off of each valve.

[0048] In this embodiment, 13 CO2 crude cold trap L1 and 13 CO2 product cold trap L2 is collecting 12 When CO2 is used, the cold trap jackets of the two are cooled by liquid nitrogen, so that 13 CO2 solidifies into a solid, that is, after the collection is completed, the cold trap is evacuated. 13 CO2 crude cold trap L1 and 13 The heating unit in the CO2 product cold trap L2 works to return the temperature to increase the pressure. At the same time, the heating unit also has the function of preventing 12 CO2 13 The inlet pipe of CO2 crude product cold trap L1 and 13 The CO2 product cold trap L2 has the function of freezing the air inlet pipe.

[0049] Please combine Figure 1 and Figure 2 The present invention also discloses a 13 CO2 production method, the production method adopts the above 13CO2 production unit, 13 The structure of the CO2 production device can be found in the above description, and no further explanation is given here. 13 The CO2 production method comprises the following steps:

[0050] S1: Catalyst is loaded into the catalytic oxidation reactor R1, and oxygen and 13 CO gas is subjected to catalytic oxidation reaction to obtain 13 CO2 crude product.

[0051] Specifically, in step S1, oxygen and 13 Before CO gas is introduced, it also includes:

[0052] S01: Under heating conditions, open the nitrogen inlet valve V1, the catalytic oxidation reactor inlet valve V4, the catalytic oxidation reactor outlet valve V5, the crude product cold trap inlet valve V7, the product cold trap inlet valve V8, the crude product cold trap outlet valve V9, the product cold trap outlet valve V10 and the vent valve V13 in sequence, pass high-purity nitrogen into the catalytic oxidation reactor R1 to purge and remove water, and pass the output gas of the ninth branch pipe into the trace water analyzer for detection until the gas moisture is qualified, and then close the nitrogen inlet valve V1 and the vent valve V13;

[0053] S02: Open the vacuum valve V12 and evacuate the catalytic oxidation reactor R1.

[0054] S2: Adoption 13 CO2 crude product is collected in cold trap L1 13 CO2 crude product is sampled and analyzed, and the content of 13 C abundance and 13 CO conversion rate and determine whether the product is qualified.

[0055] Specifically, step S2 includes:

[0056] S21: Cool down by introducing liquid nitrogen 13 CO2 crude cold trap L1 and 13 CO2 product cold trap L2, open the catalytic oxidation reactor outlet valve V5, 13 The crude CO2 enters through the dust collector B1 and filter F1 13 CO2 crude cold trap L1;

[0057] S22: Sampling and analysis are performed through the first sampling valve after the catalytic oxidation reactor outlet. 13 CO conversion rate and product 13 When the C abundance is qualified, open the product cold trap inlet valve V8 and pass the qualified product into 13 CO2 product cold trap L2.

[0058] S3: Adoption 13CO2 product cold trap L2 collects qualified products and cools the products. 13 CO2 turns into solid 13 The gas in the CO2 product cold trap L2 is evacuated and pressurized to remove 13 CO2 product cold trap L2 contains impurities and the impurity-free product is loaded into 13 CO2 product cylinder C5.

[0059] Specifically, step S3 includes:

[0060] S31: After the qualified products are collected, close the oxygen inlet valve V3, 13 Open the CO inlet valve V2 and the catalytic oxidation reactor outlet valve V5, open the product cold trap outlet valve V10, 13 Detect and analyze the gas in CO2 product cold trap L2 13 CO2 purity, 13 CO and O2 content;

[0061] S32: Yes 13 The CO2 product cold trap L2 is cooled to -90℃~-130℃, and the vacuum valve V12 is opened to 13 The CO2 product cold trap L2 is evacuated to -0.095MPa~-0.098MPa, light impurities are removed, and the vacuum valve V12 is closed; the liquid nitrogen is stopped, and the 13 The CO2 product cold trap L2 is pressurized to 0.05MPa~0.2MPa, and the gas is tested;

[0062] S33: Repeat step S32 until the product purity reaches the required level, and close the product cold trap outlet valve V10.

[0063] Furthermore, step S3 also includes:

[0064] S34: Open the vacuum valve V12 and the product cylinder inlet valve V15, evacuate the product cylinder until the absolute pressure reaches below 10Pa, close the vacuum valve V12, and 13 Increase the pressure of CO2 product cold trap L2 to 0.2MPa~7MPa, open the product cold trap outlet valve V10 and the product cylinder inlet valve V15, 13 The CO2 product is filled into the product cylinder;

[0065] S35: 13 The CO2 crude product cold trap L1 is pressurized to 0.2MPa~7MPa, and the crude product cold trap outlet valve V9 and crude product cylinder inlet valve V14 are opened. 13 The crude CO2 is charged into the crude product cylinder.

[0066] In this embodiment, the input to the catalytic oxidation reactor R1 13The flow rate of CO is 0.01kg / h~2kg / h; the oxygen and 13 The volume ratio of CO is 1.01-1.2; the catalyst in the catalytic oxidation reactor R1 uses one or more of Pt, Pd, Cu, Co, and Ir as active components, and uses one or more of aluminum oxide, titanium oxide, zinc oxide, and cerium oxide as carriers.

[0067] The following is a specific example 13 The CO2 production method is further described.

[0068] First, the catalyst is loaded into the catalytic oxidation reactor R1, and the Figure 1 The pipe and container arrangement shown is connected 13 For the CO2 production device, nitrogen is introduced to maintain pressure and detect leaks. After ensuring that the device is airtight and leak-free, all valves are set to the closed state. Heat the catalytic oxidation reactor R1 and set the temperature to 100°C to 300°C. Open the nitrogen inlet valve V1, the catalytic oxidation reactor inlet valve V4, the catalytic oxidation reactor outlet valve V5, the crude product cold trap inlet valve V7, the product cold trap inlet valve V8, the crude product cold trap outlet valve V9, the product cold trap outlet valve V10 and the vent valve V13. Purge with 99.999% high-purity nitrogen with a nitrogen pressure of 0.1MPa to 0.5MPa and a flow rate of 1L / min to 10L / min. Nitrogen enters the trace water analyzer from the sampling port (i.e., the output gas of the ninth branch pipe). After the water content in the gas is measured to be lower than 10ppm, close the nitrogen inlet valve V1 and the vent valve V13, open the vacuum valve V12, evacuate the system to an absolute pressure of less than 10Pa, and close the vacuum valve V12 to remove the non-reactive gas in the catalytic oxidation reactor R1.

[0069] Heat the catalytic oxidation reactor R1 to a temperature of 100°C to 350°C, open the oxygen inlet valves V3 and 13 CO inlet valve V2, oxygen and 13 CO, catalytic oxidation reactor R1 pressure is 0.1MPa~0.5MPa, liquid nitrogen is introduced to cool 13 The CO2 crude product cold trap L1 and the product cold trap are set to -80℃~-120℃, and the catalytic oxidation reactor inlet valve V4 and catalytic oxidation reactor outlet valve V5 are opened to catalytically oxidize the obtained 13 After the crude CO2 passes through the dust collector B1 and the filter F1, the crude product cold trap inlet valve V7 is opened to start collecting the crude product. At the same time, the first sampling valve V6 is opened to analyze and detect from the sampling port. 13 CO conversion rate is greater than 95%, 13 CO2 13 When the C abundance is greater than 98%, close the crude product cold trap inlet valve V7, open the product cold trap inlet valve V8, and collect 13CO2 products.

[0070] 13 After CO2 product cold trap L2 is collected, close the oxygen inlet valve V3, 13 The CO inlet valve V2 and the catalytic oxidation reactor outlet valve V5 are opened, and the product cold trap outlet valve V10 is opened. 13 Detect and analyze the gas in CO2 product cold trap L2 13 CO2 purity, 13 CO and O2 content. 13 The temperature of CO2 product cold trap L2 is lowered to -90℃~-130℃, and the vacuum valve V12 is opened to 13 The CO2 product cold trap L2 is evacuated to -0.095MPa~-0.098MPa to remove light impurities and close the vacuum valve V12. Stop the liquid nitrogen and 13 CO2 product cold trap L2 is pressurized to 0.05MPa~0.2MPa, and the gas is tested until the purity is greater than 99.8%. Otherwise, the cooling, vacuuming and pressurization operations are repeated until 13 When the CO2 purity is greater than 99.8%, close the product cold trap outlet valve V10.

[0071] Open the vacuum valve V12 and the product cylinder inlet valve V15, evacuate the product cylinder until the absolute pressure reaches below 10Pa, close the vacuum valve V12, and 13 Increase the pressure of CO2 product cold trap L2 to 0.2MPa~7MPa, open the product cold trap outlet valve V10 and the product cylinder inlet valve V15, 13 The CO2 product is filled into the product cylinder.

[0072] Likewise, 13 The CO2 crude product cold trap L1 is pressurized to 0.2MPa~7MPa, and the crude product cold trap outlet valve V9 and crude product cylinder inlet valve V14 are opened. 13 The crude CO2 is filled into the crude product cylinder, and then the 13 CO2 products and 13 CO2 crude product.

[0073] Implementation of the present invention 13 The CO2 production device and production method can at least achieve the following beneficial effects:

[0074] 1) Suitable for small batch production of stable isotopes, with low equipment investment, simple operation, high product yield, low cost and good economy;

[0075] 2) Production 13 CO2 purity is greater than 99.8%, 13 The C isotope abundance is greater than 98%, and the product purity and abundance meet the application requirements;

[0076] 3) Production 13 CO2, 13 The CO conversion rate is greater than 95%, making full use of the expensive 13CO raw material, with high product yield and low cost;

[0077] 4) The production and purification methods used effectively remove 13 Light components such as CO, O2, and N2 have less product loss during purification, effectively reducing production costs;

[0078] 5) CO2 is turned into solid under low temperature conditions and then removed by vacuum. 13 Light components such as CO, O2, and N2 can reduce the total content of the above impurities to less than 0.2%;

[0079] 6) Nitrogen purging is performed before the reaction to remove moisture from the reaction system, so that the water content in the product is less than 10 ppm, thereby ensuring the quality of the product and preventing water from freezing in the pipeline and clogging the pipeline;

[0080] 7) It avoids the high energy consumption of traditional distillation methods and reduces the amount of cold and heat consumed in the production process;

[0081] 8) The device is suitable for the production method of the present invention, and the purity is greater than 99.8%. 13 C isotope abundance greater than 98% 13 CO2.

[0082] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0083] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A 13 The CO2 production device is characterized in that It comprises a catalytic oxidation reactor for loading catalyst and providing a catalytic oxidation reaction site, a nitrogen cylinder connected to the input end of the catalytic oxidation reactor, 13 A CO gas cylinder and an oxygen cylinder are arranged at the output end of the catalytic oxidation reactor and one of them is connected to the output end of the catalytic oxidation reactor. 13 CO2 crude cold trap and 13 CO2 product cold trap, and for holding 13 CO2 crude 13 CO2 crude product cylinders and for 13 CO2 products 13 CO2 product cylinders, 13 The output end of the CO2 crude product cold trap is 13 The output end of the CO2 product cold trap merges and flows through the merging pipe with 13 CO2 crude cylinders and 13 The output end of the catalytic oxidation reactor is also connected to the analysis equipment; the output end of the confluence pipe is also connected to the analysis equipment, the vacuum device and the venting device; the catalytic oxidation reactor is provided with a first heating unit, 13 The CO2 crude product cold trap is equipped with a second heating unit and a first liquid nitrogen cooling unit. 13 The CO2 product cold trap is provided with a third heating unit and a second liquid nitrogen cooling unit.

2. according to claim 1 13 The CO2 production device is characterized in that The input end of the catalytic oxidation reactor is connected to a first main pipe, and the end of the first main pipe away from the catalytic oxidation reactor is respectively connected to a first branch pipe, a second branch pipe and a third branch pipe, the first branch pipe is connected to a nitrogen cylinder, the second branch pipe is connected to a nitrogen cylinder, and the third branch pipe is connected to a nitrogen cylinder. 13 The output end of the catalytic oxidation reactor is connected to the second main pipe, and the end of the second main pipe away from the catalytic oxidation reactor is respectively connected to the fourth branch pipe, the fifth branch pipe and the sixth branch pipe, the fourth branch pipe is used to be connected to the detection port of the analysis equipment, the fifth branch pipe is connected to the detection port of the analysis equipment, and the fifth branch pipe is connected to the detection port of the analysis equipment. 13 The CO2 crude product cold trap is connected to the sixth branch pipe. 13 The CO2 product cold trap is connected; the input end of the confluence pipe is connected to 13 CO2 crude product cold trap connection 13 The crude product output pipe of CO2 crude product and 13 CO2 product cold trap connection 13 The CO2 product output pipe is connected to the output end of the confluence pipe through the crude product input pipe. 13 The crude CO2 cylinder is connected to the product outlet pipe. 13 The output end of the confluence pipe is also connected to a seventh branch pipe connected to the detection port of the analysis equipment, an eighth branch pipe connected to the vacuum device, and a ninth branch pipe connected to the venting device.

3. According to claim 2 13 The CO2 production device is characterized in that The first branch pipe is provided with a nitrogen flow meter and a nitrogen inlet valve, and the second branch pipe is provided with a 13 CO gas flow meter and 13 a CO inlet valve, an oxygen flowmeter and an oxygen inlet valve are arranged on the third branch pipe, an inlet valve of a catalytic oxidation reactor is arranged on the first main pipe, an outlet valve of a catalytic oxidation reactor, a dust collector and a filter are arranged on the second main pipe, a first sampling valve is arranged on the fourth branch pipe, a crude product cold trap inlet valve is arranged on the fifth branch pipe, a product cold trap inlet valve is arranged on the sixth branch pipe, a crude product cold trap outlet valve is arranged on the crude product output pipe, a product cold trap outlet valve is arranged on the product output pipe, a crude product cylinder inlet valve is arranged on the crude product input pipe, a product cylinder inlet valve is arranged on the product input pipe, a second sampling valve is arranged on the seventh branch pipe, a vacuum valve is arranged on the eighth branch pipe, and a vent valve is arranged on the ninth branch pipe; 13 The CO2 production device also includes a control unit for controlling the on and off of each valve.

4. according to claim 3 13 The CO2 production device is characterized in that The catalytic oxidation reactor, 13 CO2 crude cold trap, 13 The CO2 product cold trap and each pipeline are made of stainless steel; the diameter of the catalytic oxidation reactor is 10 mm ~ 50 mm; the length of the catalytic oxidation reactor is 100 mm ~ 500 mm; the filtration accuracy of the filter is 0.003μm ~ 0.5μm.

5. A 13 A method for producing CO2, characterized in that Adopting the method described in claim 4 13 The CO2 production device comprises the following steps: S1: Load the catalyst into the catalytic oxidation reactor and introduce oxygen and 13 CO gas is subjected to catalytic oxidation reaction to obtain 13 CO2 crude product; S2: Adoption 13 CO2 crude product cold trap collection 13 CO2 crude product is sampled and analyzed, and the content of 13 C abundance and 13 CO conversion rate and judging whether the product is qualified; Step S2 includes: S21: Cool down by introducing liquid nitrogen 13 CO2 crude cold trap and 13 CO2 product cold trap, open the catalytic oxidation reactor outlet valve, 13 CO2 crude product enters through dust collector and filter 13 CO2 crude cold trap; S22: Sampling and analysis are performed through the first sampling valve after the catalytic oxidation reactor outlet. 13 CO conversion rate and product 13 When the C abundance is qualified, open the product cold trap air inlet valve and pass the qualified product into 13 CO2 product cold trap; S3: Adoption 13 CO2 product cold trap collects qualified products and cools the products down. 13 CO2 turns into solid 13 The gas in the CO2 product cold trap is evacuated and pressurized to remove 13 CO2 product cold trap contains impurities and the impurity-free product is loaded into 13 CO2 product cylinders.

6. According to claim 5 13 A method for producing CO2, characterized in that In step S1, oxygen and 13 Before CO gas is introduced, it also includes: S01: Under heating conditions, the nitrogen inlet valve, the catalytic oxidation reactor inlet valve, the catalytic oxidation reactor outlet valve, the crude product cold trap inlet valve, the product cold trap inlet valve, the crude product cold trap outlet valve, the product cold trap outlet valve and the vent valve are opened in sequence, and high-purity nitrogen is passed into the catalytic oxidation reactor to purge and remove water, and the output gas of the ninth branch is passed into the trace water analyzer for detection until the gas moisture is qualified, and then the nitrogen inlet valve and the vent valve are closed; S02: Open the vacuum valve and evacuate the catalytic oxidation reactor.

7. According to claim 6 13 A method for producing CO2, characterized in that Step S3 includes: S31: After the qualified products are collected, close the oxygen inlet valve, 13 The CO inlet valve and the catalytic oxidation reactor outlet valve are opened, and the product cold trap outlet valve is opened. 13 Detection and analysis of gas in CO2 product cold trap 13 CO2 purity, 13 CO and O2 content; S32: Yes 13 The CO2 product cold trap is cooled to -90 ºC ~ -130 ºC, and the vacuum valve is opened to cool the CO2 product at low temperature. 13 The CO2 product cold trap is evacuated to -0.095 MPa ~ -0.098 MPa, light impurities are removed, and the vacuum valve is closed; liquid nitrogen is stopped, and the 13 The CO2 product cold trap is pressurized to 0.05 MPa ~ 0.2 MPa, and the gas is tested; S33: Repeat step S32 until the product purity reaches the required level, and then close the product cold trap outlet valve.

8. According to claim 7 13 A method for producing CO2, characterized in that Step S3 also includes: S34: Open the vacuum valve and the gas inlet valve of the product cylinder, evacuate the product cylinder until the absolute pressure reaches below 10 Pa, close the vacuum valve, and 13 Increase the pressure of CO2 product cold trap to 0.2 MPa ~ 7 MPa, open the product cold trap outlet valve and product cylinder inlet valve, 13 The CO2 product is filled into the product cylinder; S35: 13 Increase the pressure of the CO2 crude cold trap to 0.2 MPa ~ 7 MPa, open the crude cold trap outlet valve and the crude cylinder inlet valve, and 13 The crude CO2 is charged into the crude product cylinder.

9. The method according to claim 8 13 A method for producing CO2, characterized in that Input to the catalytic oxidation reactor 13 The flow rate of CO is 0.01 kg / h ~ 2 kg / h; the oxygen and 13 The volume ratio of CO is 1.01 to 1.2; the catalyst in the catalytic oxidation reactor uses one or more of Pt, Pd, Cu, Co, and Ir as active components, and uses one or more of aluminum oxide, titanium oxide, zinc oxide, and cerium oxide as carriers.

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