Vertical oxidative combustion collection system for sediment or biological radioactive organic carbon tritium sample and use method of vertical oxidative combustion collection system

Abstract

The invention relates to a vertical oxidative combustion collection system for sediment or biological radioactive organic carbon tritium samples and a use method thereof, and the vertical oxidative combustion collection system comprises a vertical oxidative combustion device which is used for performing oxidative combustion on the samples and catalyzing the samples into to-be-separated products; the sample collecting device comprises a water vapor trapping module used for collecting tritium samples; the carbon capture module is used for collecting a 14C sample; the rear protection module is used for discharging waste gas, collecting waste liquid and preventing external air from interfering with sample collection. The collection port is arranged below the collection container, so that tritium samples and 14C samples in combustion products can be collected more thoroughly under the action of gravity, the tritium samples can be prevented from entering the 14C sample collection module, and the 14C samples can be prevented from entering the rear protection module; more importantly, tritium samples and 14C samples remaining in the collection module can be thoroughly removed and collected through a nitrogen blowing method or an inert gas blowing method, and the memory effect is avoided.

Description

Technical Field

[0001] The invention relates to a sample combustion collection technology, and in particular to a vertical oxidation combustion collection system for sediment or biological radioactive organic carbon tritium samples and a use method thereof. Background Art

[0002] Nuclear facilities will release a certain amount of tritium (T or 3 H) and 14 C, which are mainly present in the environment as HTO and carbon dioxide ( 14 CO2) in the form of ecological cycles and corresponding metabolic processes. Therefore, by monitoring the tritium and 14 C content to assess the area affected by tritium and 14 C. The degree of pollution.

[0003] Currently commonly used tritium and 14 In the C analysis method, the sample needs to be converted into a liquid state and then measured using a liquid scintillation counter after enrichment to increase the tritium and 14 The accuracy of C measurement and the avoidance of tritium and 14 The measurement accuracy is affected by the low C content. At this time, it is necessary to consider how to collect the sample in liquid state to avoid memory effects and insufficient collection.

[0004] The publication number CN106969953A published on July 21, 2017, entitled "An organic tritium carbon sample preparation device and its oxidation combustion method", discloses an organic tritium carbon sample preparation device and its oxidation combustion method, which includes a reaction working tube, an oxidation combustion furnace, and an absorption device; the reaction working tube includes a tube body, a first air inlet, a second air inlet, and an air outlet; the oxidation combustion furnace is provided with a heating zone, which is divided into a catalytic reaction zone, a sample stacking zone, and a sample recovery zone in sequence, and a temperature controller is provided at the bottom; the reaction working tube is horizontally arranged in the oxidation combustion furnace, the tube body passes through the heating zone, and the air outlet is connected to the absorption device; the absorption device includes a collection bottle and a low-temperature cold trap, the collection bottle is arranged in the low-temperature cold trap, and the air outlet is connected to the collection bottle. Carbon dioxide and water vapor are introduced into the collection bottle with nitrogen from the air outlet, and at the same time, the circulating water tank drives the coolant in the box body to flow from the coolant introduction pipe into the coolant conduit, and circulates from the coolant conduit through the coolant outlet pipe to the circulating water tank. The coolant circulates in the coolant conduit surrounding the outside of the collection bottle, so that the temperature outside the collection bottle is maintained at a stable low temperature. Carbon dioxide and water vapor are pre-condensed in the collection bottle and can be collected and tested for composition. The tritium sample generated by the sample is collected by cold trap condensation, and the carbon sample is absorbed by bubbling sodium hydroxide solution and then measured by liquid scintillation. However, the above tritium and carbon samples will have memory effects or incomplete collection. Summary of the invention

[0005] In order to solve the problems existing in the above-mentioned prior art, the object of the present invention is to provide a vertical oxidation combustion collection system for sediment or biological radioactive organic carbon tritium samples.

[0006] The present invention discloses a vertical oxidation combustion collection system for sediment or biological radioactive organic carbon tritium samples, comprising: a vertical oxidation combustion device for oxidizing and burning the sample and catalyzing it into a product to be separated; a sample collection device for collecting tritium samples and 14 C sample, the tritium sample includes tritium water, the 14 Sample C includes 14 C carbon dioxide and alkali solution formed product, the sample collection device comprises: a water vapor capture module, comprising a first blowing part, a first collecting port, a first collecting container and a first connecting part, the first collecting container is connected to the vertical oxidation combustion device through the first connecting part, and the first collecting port is connected to the bottom of the first collecting container, which is used to discharge the contents of the first collecting container from the first collecting container under the action of gravity, the first blowing part is connected to the top of the first collecting container, which is used to blow the residue after the first collecting container discharges the contents of the first collecting container from the first collecting port; a carbon capture module, comprising a second blowing part, a second collecting port, a second collecting container and a second connecting part, the second collecting container is connected to the first collecting container through the second connecting part, and The second collecting port is connected to the bottom of the second collecting container, and is used to discharge the contents of the second collecting container from the second collecting container under the action of gravity. The second blowing part is connected to the top of the second collecting container, and is used to blow out the residue after the second collecting container discharges the contents of the second collecting container from the second collecting container through the second collecting port; the post-protection module includes an exhaust part, a third collecting port, a third collecting container and a third connecting part. The third collecting container is connected to the second collecting container through the third connecting part, and the third collecting port is connected to the lower part of the third collecting container, and is used to discharge the contents of the third collecting container from the third collecting container under the action of gravity. The exhaust part is connected to the third collecting container, and is used to discharge the gas in the third collection container and prevent air backflow.

[0007] Preferably, the vertical oxidation combustion device comprises: a combustion oxidation module, the combustion oxidation module comprises a vertical detachable combustion tube, at least two air inlet pipes, an air introduction part and a heater; the combustion tube comprises a base and a fixed part, the base can be separated or combined with the fixed part by lifting, and the combustion tube is provided with a combustion chamber which is opened and closed by lifting the base and the fixed part; the air inlet pipes extend into the combustion chamber from the top and the bottom respectively, and are used to introduce combustion-supporting gas into the combustion chamber in the up and down directions respectively, so that the combustion-supporting gas forms a vortex to promote the full combustion of the sample to form a first product; the air introduction part is arranged at the top of the fixed part, and is used to introduce the first product; the heater is sleeved on the outside of the combustion tube, and is used to make the sample reach the ignition point and burn by heating; an oxidation catalytic module, the oxidation catalytic module is connected to the air introduction part, and is used to make the first product be further oxidized and catalyzed to form a second product; a three-way catalytic module, the three-way catalytic module is connected to the oxidation catalytic module, and is used to make the second product further harmless through redox reaction and become the product to be separated.

[0008] Preferably, the heater includes at least one heating part and an air cooling part, the heating part is sleeved on the outer side of the combustion tube, and is used to make the sample reach the ignition point and burn by heating, the air cooling part includes a shell and an air cooler, the shell is sleeved on the outer side of the combustion tube, is a double-layer shell with a cavity between the double layers, and the air outlet and air inlet of the air cooler are connected to the cavity between the double-layer shells.

[0009] Preferably, there are two air intake pipes, one of which extends into the combustion chamber from the top of the fixing portion or extends into the combustion chamber from the side of the fixing portion, and the other air intake pipe extends into the combustion chamber from the base.

[0010] Preferably, the oxidation catalytic module includes a foam copper mesh whose surface component is copper oxide, and a first quartz filter. The foam copper mesh is located in the channel where the first product flows from the air inlet portion to the three-way catalytic module, and is used to allow the first product to be catalytically oxidized by copper oxide to form the second product when passing through the heated foam copper mesh. The first quartz filter is located between the foam copper mesh and the combustion chamber, and is used to prevent the foam copper mesh and copper oxide from falling into the combustion chamber.

[0011] Preferably, the heater further comprises another heating part, which is sleeved on the outer side of the air ducting part and is used to form copper oxide on the surface of the foam copper mesh by heating; the temperature of each heating part is independently controlled.

[0012] Preferably, the three-way catalytic module includes a platinum-rhodium-palladium three-way catalyst, a second quartz filter and a quartz catalytic tube, one end of the quartz catalytic tube is connected to the air induction portion, the platinum-rhodium-palladium three-way catalyst is located in the quartz catalytic tube, and the second quartz filter is located at one end of the platinum-rhodium-palladium three-way catalyst close to the air induction portion, for preventing the platinum-rhodium-palladium three-way catalyst from moving along the quartz catalytic tube toward the air induction portion.

[0013] Preferably, the first collecting container comprises an inner tube and an outer condenser tube, the inner tube is connected to the vertical oxidation combustion device through the first connecting portion, and the outer condenser tube is sleeved on the outside of the inner tube.

[0014] Preferably, the inner tube is connected to the second collecting container through the second connecting portion, and the content in the second collecting container includes alkaline solution.

[0015] Preferably, the first blowing part adopts a nitrogen blowing method or an inert gas blowing method; the second blowing part adopts a nitrogen blowing method or an inert gas blowing method.

[0016] The present invention also provides a method for using the vertical oxidation combustion collection system for sediment or biological radioactive organic carbon tritium samples described in any of the above technical solutions, comprising the following steps: step one, placing the sample into the vertical oxidation combustion device, and forming a product to be separated after combustion, oxidation, and catalysis; step two, allowing the product to be separated to enter the inner tube through the first connecting part, and after condensation through the external condenser, enter the second collection container through the second connecting part, open the first collecting port to discharge the contents in the first collecting container, and then use the nitrogen or inert gas in the first blowing part to blow out the inner tube from the first collecting port to discharge the contents in the first collection container. The residue after the contents are removed; step three, part of the product to be separated that enters the second collecting container is absorbed by alkali solution, and after being completely absorbed, it enters the third collecting container through the third connecting part, and then the second collecting port is opened to discharge the contents in the second collecting container, and then the nitrogen or inert gas in the second blowing part is used to blow out the second collecting container from the second collecting port to discharge the residue after the contents in the second collecting container are removed; step four, the remaining part of the product to be separated that enters the third collecting container is discharged through the third collecting port as the contents in the third collecting container, and part is discharged through the exhaust part.

[0017] Beneficial Effects

[0018] The vertical oxidation combustion collection system for sediment or biological radioactive organic carbon tritium samples of the present invention has the advantage that by arranging the collection port below the collection container, the tritium sample and the tritium sample in the combustion product can be separated by gravity. 14C sample is collected more thoroughly and tritium sample can be prevented from entering 14 C-type collection module, avoid 14 C sample enters the post-protection module; more importantly, the nitrogen blowing method or the inert gas blowing method can completely remove and collect the residual tritium sample and 14 C sample to avoid the occurrence of memory effect. At the same time, the residue is blown out to the collection port by nitrogen blowing or inert gas blowing, which is conducive to the complete collection of the sample. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 The structure of the vertical oxidation combustion collection system for sediment or biological radioactive organic carbon tritium samples described in the present invention is shown in FIG. Figure 1 ;

[0020] Figure 2 The structure of the vertical oxidation combustion collection system for sediment or biological radioactive organic carbon tritium samples described in the present invention is shown in FIG. Figure 2 ;

[0021] Figure 3 A schematic diagram of a vertical oxidation combustion device for tritium carbon in sediments and organisms according to the present invention Figure 1 ;

[0022] Figure 4 A schematic diagram of a vertical oxidation combustion device for tritium carbon in sediments and organisms according to the present invention Figure 2 .

[0023] Description of reference numerals:

[0024] 100 vertical oxidation combustion device 111 combustion tube 1111 base

[0025] 1112 fixing part 1113 combustion chamber 112 intake pipe

[0026] 113 air bleed section 114 heater 1141 heating section

[0027] 121 Foam copper mesh 122 First quartz filter 131 Platinum-rhodium-palladium three-way catalytic converter

[0028] 132 second quartz filter 133 quartz catalytic tube 210 water vapor capture module

[0029] 211 first blowing part 212 first collecting port 213 first collecting container

[0030] 214 first connection part 220 carbon capture module 221 second blowing part

[0031] 222 second collection port 223 second collection container 224 second connection portion

[0032] 230 rear protection module 231 exhaust part 232 third collection port

[0033] 233 third collection module 234 third connection part DETAILED DESCRIPTION

[0034] The present invention provides a vertical oxidation combustion collection system for sediment or biological radioactive organic carbon tritium samples, comprising: a vertical oxidation combustion device 100, used to oxidize and burn the sample and catalyze it into a product to be separated; a sample collection device 200, used to collect tritium samples and 14 C sample, the tritium sample includes tritium water, the 14 Sample C includes 14The product formed by CO2 and alkali solution, the sample collection device 200 includes: a water vapor capture module 210, including a first blowing part 211, a first collecting port 212, a first collecting container 213 and a first connecting part 214, the first collecting container 213 is connected to the vertical oxidation combustion device 100 through the first connecting part 214, and the first collecting port 212 is connected to the bottom of the first collecting container 213, which is used to discharge the contents of the first collecting container from the first collecting container 213 under the action of gravity, the first blowing part 211 is connected to the top of the first collecting container 213, which is used to blow out the residue after the first collecting container 213 discharges the contents of the first collecting container from the first collecting port 212; a carbon capture module 220, including a second blowing part 221, a second collecting port 222, a second collecting container 223 and a second connecting part 224, the second collecting container 223 is connected to the first collecting container 213 through the second connecting part 224 The second collecting port 222 is connected to the bottom of the second collecting container 223, and is used to discharge the contents of the second collecting container from the second collecting container 223 under the action of gravity. The second blowing portion 221 is connected to the top of the second collecting container 223, and is used to blow out the residue after the second collecting container 223 discharges the contents of the second collecting container from the second collecting container from the second collecting port 222; the post-protection module 230 includes an exhaust portion 231, a third collecting port 232, a third collecting container 233 and a third connecting portion 234. The third collecting container 233 is connected to the second collecting container 223 through the third connecting portion 234, and the third collecting port 232 is connected to the lower portion of the third collecting container 233, and is used to discharge the contents of the third collecting container from the third collecting container 233 under the action of gravity. The exhaust portion 231 is connected to the third collecting container 233, and is used to discharge the gas in the third collecting container 233 and prevent air from flowing back.

[0035] The vertical oxidation combustion collection system for sediment or biological radioactive organic carbon tritium samples of the present invention has the advantage that by arranging the collection port below the collection container, the tritium sample and the tritium sample in the combustion product can be collected by gravity. 14 C sample is collected more thoroughly and tritium sample can be prevented from entering 14 C-type collection module, avoid 14 C sample enters the post-protection module; more importantly, the nitrogen blowing method or the inert gas blowing method can completely remove and collect the residual tritium sample and 14 C sample to avoid the occurrence of memory effect. At the same time, the residue is blown out to the collection port by nitrogen blowing or inert gas blowing, which is conducive to the complete collection of the sample.

[0036] The first connection part 214, the second connection part 224, the third connection part 234, the first collection port 212, the second collection port 222, the third collection port 232, the first air blowing part 211 and the second air blowing part 221 may be provided with opening and closing valves. When the valves are opened, the first connection part 214, the second connection part 224, the third connection part 234 are in a connected state, the first collection port 212, the second collection port 222, the third collection port 232 are in an open state for collection, and the first air blowing part 211 and the second air blowing part 221 are in an air blowing state; when the valves are closed, the first connection part 214, the second connection part 224, the third connection part 234 are in a blocked state, the first collection port 212, the second collection port 222, the third collection port 232 are in a closed state for non-collection, and the first air blowing part 211 and the second air blowing part 221 are in an air blowing state.

[0037] Preferably, the vertical oxidation combustion device 100 comprises: a combustion oxidation module, the combustion oxidation module comprises a vertical detachable combustion tube 111, at least two air inlet pipes 112, an air induction part 113 and a heater 114; the combustion tube 111 comprises a base 1111 and a fixing part 1112, the base 1111 can be separated or combined with the fixing part 1112 by lifting, and a combustion chamber 1113 is provided in the combustion tube 111, which is opened and closed by lifting the base 1111 and the fixing part 1112; the air inlet pipe 112 extends into the combustion chamber 1113 from the upper and lower directions respectively, and is used to supply air to the combustion chamber 1113 in the upper and lower directions respectively. A combustion-supporting gas is introduced to form a vortex to promote full combustion of the sample to form a first product; the air inlet portion 113 is arranged at the top of the fixing portion 1112, and is used to introduce the first product; the heater 114 is sleeved on the outside of the combustion tube 111, and is used to make the sample reach the ignition point and burn by heating; an oxidation catalytic module, the oxidation catalytic module is connected to the air inlet portion 113, and is used to further oxidize and catalyze the first product to form a second product; a three-way catalytic module, the three-way catalytic module is connected to the oxidation catalytic module, and is used to further render the second product harmless through a redox reaction and become the product to be separated.

[0038] In a specific implementation, the air inlet pipe 112 can be set to 2-4 pieces. For example, 1-2 pieces can be set at the upper part of the fixed part 1112, all of which are introduced from the outside of the fixed part 1112 through the shell of the fixed part 1112 to the top of the combustion chamber 113 and make the combustion-supporting gas flow downward (that is, the fixed part 112 points to the direction of the base 1111); 1-2 pieces can be set on the base 1111, all of which are passed through the base 1111 from the outside of the base 1111 to enter the bottom of the combustion chamber 1113 and make the combustion-supporting gas flow upward (that is, the base 1111 points to the direction of the fixed part 1112). Specifically, the sample burns under the support of oxygen in the air inlet pipe 112 set on the base 1111, and is further fully burned after mixing with the oxygen in the air inlet pipe 112 at the upper part of the fixed part 1112 to form the first product. The heater 114 can heat the sample by heat conduction. In order to realize the heating function of the heater 114, the heater 114 and the position where it is installed on the combustion tube 1113 can adopt the heating components in the prior art and select the installation position in the prior art. Those skilled in the art can select the heating components and installation positions in the prior art according to actual needs. The first product is catalytically oxidized by the oxidation catalytic module to form the second product, and then further detoxified by the three-way catalytic module through oxidation-reduction reaction to form the product to be separated.

[0039] The combustion-supporting gas is preferably oxygen. Due to the high efficiency and thoroughness of the combustion and post-treatment (oxidation, catalysis, reduction), the sample processing volume is not less than 100g of biological radioactive samples, or 200g of sediment / soil samples each time.

[0040] The vertical oxidation combustion device for sediment or biological radioactive organic carbon tritium sample described in the present invention has the advantages that, taking oxygen as the combustion-supporting gas, the sample on the base is heated by oxygen, and after reaching the ignition temperature, it burns rapidly, and the oxidation produces gas (mainly including carbon monoxide (CO, including 14 CO), hydrocarbons (mainly incompletely burned hydrocarbons CH n , including 14 C Hydrogen Compounds 14 CH n , Carbon tritium compound CT n , 14 C tritium compounds 14 CT n , where the subscript n represents the number of atoms, the same below), carbon dioxide (CO2, containing 14 CO2), water (H2O, including HTO and T2O) and particulate matter (mainly incompletely burned hydrocarbons C n Hm O k , including 14 C n H m O k , C n T m O k and 14 C n T n O k etc. particles; wherein the subscripts n, m and k represent the number of atoms, the same below); in the middle of the combustion tube: the gas and particles rise with the airflow, continue to burn under the action of oxygen, release a large amount of heat to accelerate combustion; in the upper part of the combustion tube, the pure oxygen airflow flowing downward is added through the air inlet pipe, and intersects with the rising airflow, which can effectively supplement oxygen to accelerate combustion; at the same time, the pure oxygen airflow flowing downward intersects with the rising airflow, which will inevitably form a vortex microenvironment in the upper and middle areas of the combustion tube, and some of the particles that are not fully burned will also boil and burn like the ups and downs of the airflow, which is more conducive to the complete combustion of the sample. In addition to oxygen, in the system where other combustion-supporting gases exist, such as hydrogen, alkanes are combustion-supporting gases or one of the combustion-supporting gases, the above-mentioned vortex environment can also be formed by the scheme of the present invention to promote the combustion of the corresponding system samples. In addition, the present invention is based on a three-stage cascade modular oxidation catalytic design, which effectively overcomes the disadvantages of incomplete dual-zone combustion, and the conversion efficiency of tritium water and carbon dioxide is higher. The vertical dual-path oxygen combustion-supporting design based on the boiling combustion principle has high heat utilization efficiency and more complete combustion.

[0041] Preferably, the heater 114 includes at least one heating part 1141 and an air cooling part. The heating part 1141 is sleeved on the outer side of the combustion tube 111, and is used to make the sample reach the ignition point and burn by heating. The air cooling part includes a shell and an air cooler. The shell is sleeved on the outer side of the combustion tube 111, is a double-layer shell with a cavity between the double layers, and the air outlet and air inlet of the air cooler are connected to the cavity between the double-layer shells.

[0042] In specific implementation, the heating part 1141 is sleeved on the outer side of the combustion tube 111, and its sleeve position needs to achieve this function, that is, the sample reaches the ignition point and burns by heating. Those skilled in the art can select the heater used in the heating part and the sleeve position of the heating part 1141 according to the existing technology and actual needs. After the air-cooling part (not shown in the figure) is started, air (such as cold air) returns to the air-cooling part from the air inlet (not shown in the figure) of the air-cooling part through the cavity between the double-layer shells and from the air outlet (not shown in the figure) of the air-cooling part, and is sent to the air inlet of the air-cooling part again after processing (such as cooling). The air-cooling part can adopt the air-cooling system in the prior art, and those skilled in the art can select the air-cooling system in the prior art according to actual needs.

[0043] Preferably, there are two air intake pipes 112 , one of which extends into the combustion chamber 1113 from the top of the fixing portion 1112 or extends into the combustion chamber 1113 from the side of the fixing portion 1112 , and the other air intake pipe 112 extends into the combustion chamber 1113 from the base 1111 .

[0044] In a specific implementation, when one of the air intake pipes 112 extends from the top of the fixed portion 1112 into the combustion chamber 1113, and the other air intake pipe 112 extends from the base 1111 into the combustion chamber 1113, the sample burns to form gas and particulate matter under the action of the combustion-supporting gas (oxygen) in the air intake pipe 112 and the heater (heating the sample to the ignition point to cause the sample to burn), and the gas and the particulate matter rise to the middle of the combustion chamber for further combustion, and the gas and a small amount of particulate matter after further combustion form a vortex in the upper part of the combustion chamber with the combustion-supporting gas (oxygen) flowing from the top of the fixed portion 1112 in the air intake pipe 112 toward the base 111 and are fully burned. When the air intake pipe 112 extends from the side of the fixed portion 1112 into the combustion chamber 1113, the principle is the same as above. When the air intake pipe 112 extends from the top of the fixing part 1112 into the combustion chamber 1113, it can extend from the upper part or upper opening of the fixing part 1112 and be fixed by a sealing component such as a plug, a cover or a plug. The sealing component is provided with a through hole (not shown in the figure) that can accommodate the air intake pipe 112 and the air induction part 113. The matching relationship and position relationship of the sealing component, the air intake pipe 112 and the air induction part 113 at the upper part or upper opening of the fixing part 1112 adopt the position relationship and matching relationship in the prior art. Those skilled in the art can select the position relationship and matching relationship in the prior art according to actual needs, and open a through hole on the double-layer shell as appropriate. When the air intake pipe 112 extends from the side of the fixing part 1112 into the combustion chamber 1113, a through hole needs to be opened on the double-layer shell.

[0045] Preferably, the oxidation catalytic module includes a foam copper mesh 121 whose surface component is copper oxide, and a first quartz filter 122. The foam copper mesh 121 is located in the channel where the first product flows from the air inlet portion 113 to the three-way catalytic module, and is used to allow the first product to be catalytically oxidized by copper oxide to form the second product when passing through the heated foam copper mesh 121. The first quartz filter 122 is located between the foam copper mesh 121 and the combustion chamber 1113, and is used to prevent the foam copper mesh 121 and copper oxide from falling into the combustion chamber 1113.

[0046] In a specific implementation, the foam copper mesh 121 is oxidized at high temperature before the reaction, and CuO is generated on the surface. When the sample reacts, copper oxide plays the dual role of oxidant and catalyst, so that the sample burns to form a further combustible gas (carbon monoxide (CO, containing 14 CO), hydrocarbons (CH n , unburned hydrocarbon components, including 14 CH n , CT n , 14 CT n ) accelerates combustion and generates carbon dioxide (CO2, containing 14 CO2), water (H2O, including HTO and T2O), its combustion rate reaches 90%. At the same time, at high temperature, copper oxide can also catalyze carbon monoxide (CO,, including 14 CO) is oxidized to carbon dioxide or carbon-14 carbon dioxide (CO2, containing 14 CO2), catalytic hydrocarbons (CH n , including 14 CH n , CT n , 14 CT n ) reacts with O2 to produce carbon dioxide (CO2, containing 14 CO2), (H2O, including HTO, T2O), or carbon monoxide (CO, including 14 CO) is oxidized by CuO to produce carbon dioxide (CO2, containing 14 CO2), at which point CuO is reduced to Cu. After further catalytic oxidation of CuO, the combustion rate of the sample can reach 90%, reducing the working pressure of the three-way catalytic module.

[0047] Preferably, the heater 114 further includes another heating portion 1141, which is sleeved on the outer side of the air ducting portion 113 and is used to form copper oxide on the surface of the foam copper mesh 121 by heating; the temperature of each heating portion 1141 is independently controlled.

[0048] In specific implementation, the heating part 1141 is sleeved on the outer side of the air inlet part 113, and its sleeve position needs to achieve this function, even if the foam copper mesh generates copper oxide at high temperature, those skilled in the art can select the heater used in the heating part and the sleeve position of the heating part 1141 according to existing technology and actual needs. The temperature of each heating part 1141 is independently controlled by a separate control unit, which is conducive to the selection of different sample reaction conditions.

[0049] Preferably, the three-way catalytic module includes a platinum-rhodium-palladium three-way catalyst 131, a second quartz filter 132 and a quartz catalytic tube 133, one end of the quartz catalytic tube 133 is connected to the air inlet portion 113, the platinum-rhodium-palladium three-way catalyst 131 is located in the quartz catalytic tube 133, and the second quartz filter 132 is located at one end of the platinum-rhodium-palladium three-way catalyst 131 close to the air inlet portion 113, and is used to prevent the platinum-rhodium-palladium three-way catalyst 131 from moving along the quartz catalytic tube 133 toward the air inlet portion 113.

[0050] In a specific implementation, the platinum-rhodium-palladium three-way catalyst 131 provides a surface having a platinum-rhodium-palladium three-way catalyst, and the carrier for carrying the platinum-rhodium-palladium three-way catalyst is a porous ceramic, and the platinum-rhodium-palladium three-way catalyst enables the oxidation-reduction reaction of the gas oxidized and catalyzed by the oxidation catalytic module to be carried out efficiently at a relatively low temperature. In the oxidation-reduction reaction process, carbon monoxide (CO, containing 14 CO), hydrocarbons (CH n , incompletely burned fuel components, including 14 CH n ), carbon tritium compounds (CT n , including 14 CT n ) and nitrogen oxides (NO n These harmful gases are converted into relatively harmless carbon dioxide (CO2, containing 14 CO2), water (H2O, including tritium water HTO and T2O) and nitrogen (N2). 14 CO), hydrocarbons (CH n , including 14 CH n , CT n , 14 CT n ) is oxidized to generate carbon dioxide (CO, containing 14 CO), water (H2O, including HTO and T2O), nitrogen oxides (NO n) is reduced to nitrogen (N2) under the action of the catalyst. This is a reduction process. Through this redox process, the oxidized catalytic gas is rendered harmless, easy to collect and avoids environmental pollution caused by gas leakage. And nitrogen oxides (NO n ) is converted into nitrogen (N2), which effectively reduces the acidity of water (tritium water) and the quenching effect and color effect of subsequent liquid scintillation, and improves the measurement efficiency of tritium carbon.

[0051] Preferably, the first collecting container 213 includes an inner tube 2131 and an outer condenser tube 2132 , the inner tube 2131 is connected to the vertical oxidation combustion device 100 through the first connecting portion 214 , and the outer condenser tube 2132 is sleeved on the outside of the inner tube 2131 .

[0052] In a specific implementation, when the product to be separated enters the inner tube 2131 from the vertical oxidation combustion device 100 through the first connecting portion 214, the outer condenser 2132 condenses the water vapor and / or gaseous tritium water in the product to be separated and falls into the inner tube 2131. At this time, part of the nitrogen oxides NO n (If any) is also dissolved in the condensed water (tritiated water) to form the contents in the first collection container.

[0053] Preferably, the inner tube 2131 is connected to the second collecting container 223 through the second connecting portion 224, and the content in the second collecting container includes alkaline solution.

[0054] In a specific implementation, carbon dioxide and carbon-14 carbon dioxide are absorbed by the alkali solution in part of the product to be separated that enters the second collection container 223 from the inner tube 2131 through the second connection portion 221 to form the content in the second collection container. The rest of the product to be separated enters the third collection container 233.

[0055] Preferably, the first blowing part 211 adopts a nitrogen blowing method or an inert gas blowing method; the second blowing part 221 adopts a nitrogen blowing method or an inert gas blowing method.

[0056] In a specific implementation, the air flow rates of the first air blowing part 211 and the second air blowing part 221 are independent of each other.

[0057] The present invention also provides a method for using the vertical oxidation combustion collection system for sediment or biological radioactive organic carbon tritium samples described in any of the above technical solutions, comprising: step one, placing the sample into the vertical oxidation combustion device, and forming a product to be separated after combustion, oxidation, and catalysis; step two, allowing the product to be separated to enter the inner tube 2131 through the first connecting portion 214, and after condensation through the external condenser 2132, enter the second collection container 223 through the second connecting portion 224, open the first collecting port 212 to discharge the contents in the first collecting container, and then use the nitrogen or inert gas in the first blowing portion 211 to blow out the inner tube 2131 from the first collecting port 212 to discharge the contents in the first collecting container. residue; step three, part of the product to be separated entering the second collecting container 223 is absorbed by alkali solution, and after being completely absorbed, it enters the third collecting container 233 through the third connecting part 234, and then the second collecting port 222 is opened to discharge the contents in the second collecting container, and then the nitrogen or inert gas in the second blowing part 221 is used to blow out the second collecting container 223 from the second collecting port 222 to discharge the contents in the second collecting container. Residue; step four, the remaining product to be separated entering the third collecting container 233 is discharged as the contents in the third collecting container through the third collecting port 232, and part of it is discharged in the form of gas through the exhaust part 231.

[0058] The above method is simple to operate, has high collection efficiency, no memory effect, is environmentally friendly and pollution-free, and also avoids contamination and influence of the external environment on the sample through the setting of the post-protection module.

[0059] The following are embodiments of the present invention

[0060] like Figure 1 and Figure 2 As shown, in Example 1 of the present invention, a vertical oxidation combustion collection system for sediment or biological radioactive organic carbon tritium samples comprises: a vertical oxidation combustion device 100, used to oxidize and burn the sample and catalyze it into a product to be separated; a sample collection device 200, used to collect tritium samples and 14 C carbon dioxide, the sample collection device 200 includes: a water vapor capture module 210, a carbon capture module 220, and a post-protection module 230.

[0061] The water vapor capture module 210 includes a first blowing part 211, a first collecting port 212, a first collecting container 213 and a first connecting part 214. The first collecting container 213 is connected to the vertical oxidation combustion device 100 through the first connecting part 214, and the first collecting port 212 is connected to the bottom of the first collecting container 213, and is used to discharge the contents of the first collecting container from the first collecting container 213 under the action of gravity. The first blowing part 211 is connected to the top of the first collecting container 213, and is used to discharge the contents of the first collecting container from the first collecting container 213. The residue after the contents in the first collecting container are discharged is blown out from the first collecting port 212, the first collecting container 213 comprises an inner tube 2131 and an outer condenser 2132, the inner tube 2131 is connected to the vertical oxidation combustion device through the first connecting portion 214, and the outer condenser 2132 is sleeved on the outside of the inner tube 2131; a valve (not shown in the figure) is provided on the first connecting portion 214, a valve (not shown in the figure) is provided on the first collecting port 212, and a valve (not shown in the figure) is provided on the first blowing portion 211;

[0062] The carbon capture module 220 comprises a second blowing part 221, a second collecting port 222, a second collecting container 223 and a second connecting part 224. The second collecting container 223 is connected to the first collecting container 213 through the second connecting part 223. More specifically, the inner tube 2131 is connected to the second collecting container through the second connecting part 223, and the second collecting port 222 is connected to the bottom of the second collecting container 223, so as to discharge the contents of the second collecting container from the second collecting container 223 under the action of gravity. The contents of the second collecting container include alkali solution. The second blowing part 221 is connected to the top of the second collecting container 223, so as to blow out the residue after the second collecting container 223 discharges the contents of the second collecting container from the second collecting port 222. The second connecting part 224 is provided with a valve (not shown in the figure), the second collecting port 222 is provided with a valve (not shown in the figure), and the second blowing part 221 is provided with a valve (not shown in the figure).

[0063] The post-protection module 230 includes an exhaust portion 231, a third collecting port 232, a third collecting container 233 and a third connecting portion 234. The third collecting container 233 is connected to the second collecting container 223 via the third connecting portion 233, and the third collecting port 232 is connected to the lower portion of the third collecting container 233, and is used to discharge the contents of the third collecting container from the third collecting container 233 under the action of gravity. The exhaust portion 231 is connected to the third collecting container 233, and is used to discharge the gas in the third collecting container 233 and prevent air backflow. A valve (not shown in the figure) is provided on the third collecting port 232, and a valve is provided on the third connecting portion 233.

[0064] In a specific implementation, the product to be separated is generated by the vertical oxidation combustion device, and the product to be separated enters the inner tube 2131 through the first connection part 214, is condensed by the external condenser 2132, and then enters the second collection container 223 through the second connection part 224. The valve on the first connection part 214 and the valve on the second connection part 224 are closed, and the valve on the first collection port 212 is opened to discharge the contents in the first collection container. Then, the valve on the first blowing part 211 is opened to blow nitrogen from the first collection port 212 out of the inner tube 2131 to discharge the contents in the first collection container. The part of the product to be separated that enters the second collection container 223 is The product is absorbed by the alkali solution, and after being completely absorbed, it enters the third collection container 233 through the third connection part 234, the valve on the third connection part 234 is closed, the valve on the second collection port 222 is opened to discharge the contents in the second collection container, and then the valve on the second blowing part 221 is opened to blow nitrogen out of the second collection container 223 from the second collection port 222 to discharge the contents in the second collection container; of the remaining product to be separated that enters the third collection container 233, a part is discharged in the form of the contents in the third collection container by opening the valve on the third collection port 232, and a part is discharged in the form of gas through the exhaust part 231. The collected contents and residues are to be detected.

[0065] According to the present invention, the nitrogen flow rate in the first blowing section 211 is 0.15L / min-0.5L / min, and the nitrogen flow rate in the second blowing section 221 is 0.15L / min-0.5L / min. The nitrogen flow rate in the first blowing section 211 and the nitrogen flow rate in the second blowing section 221 are independently controlled by two flow meters.

[0066] like Figure 1 and Figure 3As shown, in the second embodiment of the present invention, the difference from the first embodiment is that the vertical oxidation combustion device 100 adopted comprises: a combustion oxidation module, the combustion oxidation module comprises a vertical detachable combustion tube 111, two air inlet pipes 112, an air induction part 113 and a heater 114; the combustion tube 111 comprises a base 1111 and a fixing part 1112, the base 1111 can be separated or combined with the fixing part 1112 by lifting, and the combustion tube 111 is provided with a combustion chamber 1113 which is opened and closed by lifting the base 1111 and the fixing part 1112; the air inlet pipes 112 extend into the combustion chamber 1113 from the upper and lower sides respectively, and are used to move the combustion chamber 1113 in the upper and lower directions respectively. The combustion chamber 1113 is introduced with a combustion-supporting gas, so that the combustion-supporting gas forms a vortex to promote full combustion of the sample to form a first product; the air inlet portion 113 is arranged at the top of the fixing portion 1112, and is used to introduce the first product; the heater 114 is sleeved on the outside of the combustion tube 111, and is used to make the sample reach the ignition point and burn by heating; an oxidation catalytic module, the oxidation catalytic module is connected to the air inlet portion 113, and is used to further oxidize and catalyze the first product to form a second product; a three-way catalytic module, the three-way catalytic module is connected to the oxidation catalytic module, and is used to make the second product further harmless through an oxidation-reduction reaction and become the product to be separated;

[0067] Of the two air intake pipes 112, one air intake pipe 112 extends from the side of the fixing portion 1112 into the combustion chamber 1113, and the other air intake pipe 112 extends from the base 1111 into the combustion chamber 1113;

[0068] The heater 114 includes two heating parts 1141 and an air cooling part 1142. The heating part 1141 is sleeved on the outer side of the combustion tube 111 and is used to heat the sample to reach the ignition point and burn. The air cooling part 1142 includes a shell and an air cooler. The shell is sleeved on the outer side of the combustion tube 111 and is a double-layer shell with a cavity between the double layers. The air outlet and the air inlet of the air cooler are connected to the cavity between the double-layer shells.

[0069] The oxidation catalytic module comprises a foam copper mesh 121 whose surface component is copper oxide and a first quartz filter 122. The foam copper mesh 121 is located in the channel where the first product flows from the air induction portion 113 to the three-way catalytic module, and is used to make the first product be catalytically oxidized by copper oxide to form the second product when passing through the heated foam copper mesh 121. The first quartz filter 122 is located between the foam copper mesh 121 and the combustion chamber 1113, and is used to prevent the foam copper mesh 121 and copper oxide from falling into the combustion chamber 1113.

[0070] The heater 114 further includes another heating portion 1141 , which is sleeved on the outer side of the air inlet portion 113 and is used to form copper oxide on the surface of the foam copper mesh 121 by heating; the temperature of each heating portion 1141 is independently controlled.

[0071] The three-way catalytic module includes a platinum-rhodium-palladium three-way catalyst 131, a second quartz filter 132 and a quartz catalytic tube 133, one end of the quartz catalytic tube 133 is connected to the air inlet portion 113, the platinum-rhodium-palladium three-way catalyst 131 is located in the quartz catalytic tube 133, and the second quartz filter 132 is located at one end of the platinum-rhodium-palladium three-way catalyst 131 close to the air inlet portion 113, and is used to prevent the platinum-rhodium-palladium three-way catalyst 131 from moving along the quartz catalytic tube 133 toward the air inlet portion 113.

[0072] The rest is the same as Example 1.

[0073] In specific implementation, the generation process of the product to be separated is as follows: lower the base 1111, put the sample in, and then raise the base 1111 to combine it with the fixing part 1112; control the heating temperature of the other heating part 1141 from room temperature to 800°C, with a heating rate of 10°C / min, and continuously heat the foam copper mesh 121 at a constant temperature, and use a heating device (not shown in the figure) to heat the platinum-rhodium-palladium three-way catalytic converter 131, and the heating temperature is from room temperature to 600°C, with a heating rate of 10°C / min. When the foam copper mesh 121 and the platinum-rhodium-palladium three-way catalyst 131 reach 800°C and 600°C, the combustion-supporting gas is introduced from the upper and lower sides of the combustion tube 111 through the intake pipe 112 and the heating temperature of the heating part 1141 is controlled from room temperature to 800°C, and the heating rate is 10°C / min. Then the sample is heated to the ignition point at a constant temperature, and the gas formed by the combustion of the sample is continuously heated or kept at a constant temperature, oxidized, catalyzed, and reduced until the gas is harmlessly degraded to form the product to be separated. Then, the product to be separated is collected according to the steps of Example 1.

[0074] More specifically, of the two air inlet pipes 112, the oxygen flow rate of the air inlet pipe 112 extending from the base 1111 into the combustion chamber 1113 is 0.12L / min-0.5L / min, and the oxygen flow rate of the air inlet pipe 112 extending from the side of the fixing portion 1112 into the combustion chamber 1113 is 0.12L / min-0.5L / min. The oxygen flow rates in the two air inlet pipes 112 are independently controlled by two flow meters. (The flow rates of nitrogen and oxygen required for the specific experiment are adjusted according to the organic matter and oil content in the sample)

[0075] like Figure 2 and Figure 4As shown, embodiment 3 of the present invention is different from embodiment 2 in that, of the two air intake pipes 112, one air intake pipe 112 extends from the top of the fixing portion 1112 into the combustion chamber 1113, and the other air intake pipe 112 extends from the base 1111 into the combustion chamber 1113; the rest is the same as embodiment 2.

[0076] The vertical oxidation combustion collection system for sediment or biological radioactive organic carbon tritium samples of the present invention has the advantage that the collection port is arranged below the flow path of the combustion products or used to absorb the tritium in the combustion products. 14 Below the alkaline solution of sample C, gravity can be used to separate the tritium sample and the 14 C sample is collected more thoroughly and tritium sample can be prevented from entering 14 C-type collection module, avoid 14 C sample enters the post-protection module; more importantly, the nitrogen blowing method or the inert gas blowing method can completely remove and collect the tritium sample and 14 C sample, to avoid the occurrence of memory effect and ensure that the tritium sample and 14 Sample C is collected completely.

[0077] In the description of the present invention, it is necessary to understand that the directions or positional relationships indicated by directional words such as "front, back, up, down, left, right", "lateral, vertical, horizontal" and "top, bottom" are usually based on the directions or positional relationships shown in the drawings. They are only for the convenience of describing the present invention and simplifying the description. Unless otherwise specified, these directional words do not indicate or imply that the device or element referred to must have a specific direction or be constructed and operated in a specific direction. Therefore, they cannot be understood as limiting the scope of protection of the present invention.

[0078] For those skilled in the art, various other corresponding changes and deformations can be made according to the technical solutions and concepts described above, and all of these changes and deformations should fall within the protection scope of the claims of the present invention.

Claims

1. A vertical oxidation combustion collection system for sediment or biological radioactive organic carbon tritium samples, characterized in that: include: A vertical oxidation combustion device (100) is used to oxidize and combust the sample and catalyze it into products to be separated; A sample collection device (200) is used to collect tritium samples and 14 C sample, the tritium sample includes tritium water, the 14 Sample C includes 14 C is a product formed by carbon dioxide and alkali solution, the sample collection device (200) comprises: The water vapor capture module (210) comprises a first blowing portion (211), a first collecting port (212), a first collecting container (213) and a first connecting portion (214); the first collecting container (213) is connected to the vertical oxidation combustion device (100) via the first connecting portion (214); the first collecting port (212) is connected to the bottom of the first collecting container (213) and is used to discharge the contents of the first collecting container from the first collecting container (213) under the action of gravity; the first blowing portion (211) is connected to the top of the first collecting container (213) and is used to blow out the residue after the first collecting container (213) discharges the contents of the first collecting container from the first collecting port (212); A carbon capture module (220), comprising a second blowing portion (221), a second collecting port (222), a second collecting container (223) and a second connecting portion (224); the second collecting container (223) is connected to the first collecting container (213) via the second connecting portion (224); the second collecting port (222) is connected to the bottom of the second collecting container (223) and is used to discharge the contents of the second collecting container from the second collecting container (223) under the action of gravity; the second blowing portion (221) is connected to the top of the second collecting container (223) and is used to blow out the residue after the second collecting container (223) discharges the contents of the second collecting container from the second collecting container through the second collecting port (222); The rear protection module (230) comprises an exhaust portion (231), a third collecting port (232), a third collecting container (233) and a third connecting portion (234); the third collecting container (233) is connected to the second collecting container (223) via the third connecting portion (234), and the third collecting port (232) is connected to the lower portion of the third collecting container (233) for discharging the contents of the third collecting container from the third collecting container (233) under the action of gravity; the exhaust portion (231) is connected to the third collecting container (233) for discharging the gas in the third collecting container (233) and preventing air from flowing back.

2. The vertical oxidation combustion collection system for sediment or biological radioactive organic carbon tritium samples according to claim 1, characterized in that: The vertical oxidation combustion device (100) comprises: A combustion oxidation module, the combustion oxidation module comprising a vertical detachable combustion tube (111), at least two air inlet pipes (112), an air induction part (113) and a heater (114); the combustion tube (111) comprises a base (1111) and a fixing part (1112); the base (1111) can be separated from or combined with the fixing part (1112) by lifting; the combustion tube (111) is provided with a combustion chamber (1111) which is opened and closed by lifting the base (1111) and the fixing part (1112). 113); the air inlet pipe (112) extends into the combustion chamber (1113) from the top and bottom respectively, and is used to introduce the combustion-supporting gas into the combustion chamber (1113) in the top and bottom directions respectively, so that the combustion-supporting gas forms a vortex to promote the full combustion of the sample and form a first product; the air introduction part (113) is arranged on the top of the fixing part (1112) and is used to introduce the first product; the heater (114) is sleeved on the outside of the combustion tube (111) and is used to make the sample reach the ignition point and burn by heating; An oxidation catalytic module, the oxidation catalytic module being connected to the air induction portion (113) and used for further oxidizing and catalyzing the first product to form a second product; A three-way catalytic module is connected to the oxidation catalytic module and is used to further render the second product harmless through a redox reaction and become the product to be separated.

3. The vertical oxidation combustion collection system for sediment or biological radioactive organic carbon tritium samples according to claim 2, characterized in that: The heater (114) includes at least one heating part (1141) and an air cooling part. The heating part (1141) is sleeved on the outer side of the combustion tube (111) and is used to make the sample reach the ignition point and burn by heating. The air cooling part includes a shell and an air cooler. The shell is sleeved on the outer side of the combustion tube (111) and is a double-layer shell with a cavity between the double layers. The air outlet and air inlet of the air cooler are connected to the cavity between the double-layer shells.

4. The vertical oxidation combustion collection system for sediment or biological radioactive organic carbon tritium samples according to claim 2, characterized in that: There are two air intake pipes (112), one of which extends from the top of the fixing portion (1112) into the combustion chamber (1113) or from the side of the fixing portion (1112) into the combustion chamber (1113), and the other air intake pipe (112) extends from the base (1111) into the combustion chamber (1113).

5. The vertical oxidation combustion collection system for sediment or biological radioactive organic carbon tritium samples according to claim 2, characterized in that: The oxidation catalytic module comprises a foam copper mesh (121) whose surface component is copper oxide, and a first quartz filter (122); the foam copper mesh (121) is located in a channel through which the first product flows from the air induction portion (113) to the three-way catalytic module, and is used to allow the first product to be catalytically oxidized by copper oxide to form the second product when passing through the heated foam copper mesh (121); and the first quartz filter (122) is located between the foam copper mesh (121) and the combustion chamber (1113), and is used to prevent the foam copper mesh (121) and the copper oxide from falling into the combustion chamber (1113).

6. The vertical oxidation combustion collection system for sediment or biological radioactive organic carbon tritium samples according to claim 5, characterized in that: The heater (140) further comprises another heating portion (1141), which is sleeved on the outer side of the air inlet portion (113) and is used to form copper oxide on the surface of the foam copper mesh (121) by heating; the temperature of each heating portion (1141) is independently controlled.

7. The vertical oxidation combustion collection system for sediment or biological radioactive organic carbon tritium samples according to claim 1, characterized in that: The first collecting container (213) comprises an inner tube (2131) and an outer condenser tube (2132); the inner tube (2131) is connected to the vertical oxidation combustion device (100) via the first connecting portion (214); and the outer condenser tube (2132) is sleeved on the outside of the inner tube (2131).

8. The vertical oxidation combustion collection system for sediment or biological radioactive organic carbon tritium samples according to claim 7, characterized in that: The inner tube (2131) is connected to the second collecting container (223) via the second connecting portion (224), and the content in the second collecting container includes alkaline solution.

9. The vertical oxidation combustion collection system for sediment or biological radioactive organic carbon tritium samples according to claim 1, characterized in that: The first blowing part (211) adopts a nitrogen blowing method or an inert gas blowing method; the second blowing part (221) adopts a nitrogen blowing method or an inert gas blowing method.

10. A method for using the vertical oxidation combustion collection system for sediment or biological radioactive organic carbon tritium samples according to any one of claims 1 to 9, characterized in that: Step 1: placing the sample into a vertical oxidation combustion device to form a product to be separated after combustion, oxidation and catalysis; Step 2, allowing the product to be separated to enter the inner tube (2131) through the first connecting portion (214), condense through the external condenser (2132), and then enter the second collecting container (223) through the second connecting portion (224), opening the first collecting port (212) to discharge the contents in the first collecting container, and then using the nitrogen or inert gas in the first blowing portion (211) to blow out the inner tube (2131) from the first collecting port (212) to discharge the residue after the contents in the first collecting container are discharged; Step three, part of the product to be separated entering the second collecting container (223) is absorbed by alkaline solution, and after being completely absorbed, it enters the third collecting container (233) through the third connecting portion (234), and then the second collecting port (222) is opened to discharge the contents in the second collecting container, and then the nitrogen or inert gas in the second blowing portion (221) is used to blow out the second collecting container (223) from the second collecting port (222) to discharge the residue after the contents in the second collecting container are discharged; Step 4, the remaining product to be separated that enters the third collecting container (233) is discharged through the third collecting port (232) as the contents in the third collecting container, and part is discharged through the exhaust part (231).

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