JP7004952B2 - Graphitizer, sampling / preparation system and sampling / preparation method - Google Patents

Description

The present invention relates to the field of isotope detection, and specifically to a graphitizer, a sampling / preparation system, and a sampling / preparation method.

With the development of society and the improvement of human quality of life, the demand for energy supply is increasing. In the context of sustainable development and green development, new demands have been submitted for energy supply as fossil energy reserves have declined.

Biomass energy is a kind of "carbon neutral" renewable energy. The power supply technology that puts biomass fuel directly into the furnace and burns it will be very advanced in China. According to foreign experience, mixing and burning biomass using a conventional coal-burning boiler is a better way to utilize biomass energy. This combustion method not only improves the power generation efficiency of biomass fuel, but also saves the investment cost of the infrastructure of the biomass direct combustion power plant, and is an efficient and environment-friendly energy acquisition method.

In this combustion method, it may be necessary to measure the mixing ratio of biomass. Carbon-14 is widely used as a measuring method. Carbon-14 ( ^14C ) is a radioisotope of the elemental carbon discovered by Martin Carmen and Sam Ruben in the Radiolab at the University of California, Berkeley on February 27, 1940.

Carbon-14 is produced when cosmic rays hit nitrogen atoms in the air. Since living organisms participate in the carbon cycle process around the world, the abundance of carbon-14 contained in them often matches the local atmospheric level at that time. Since fossil energy has been buried deep underground for millions of years, it contains almost zero carbon-14. Therefore, by measuring the abundance data of carbon-14 contained in carbon dioxide in the boiler smoke gas of the mixed combustion power plant that mixes and burns coal and biomass, the biomass fuel is mixed with the fuel that this power plant burns. It is possible to know whether or not the fuel is mixed and the proportion of the biomass fuel contained in the fuel.

Radiocarbon dating based on carbon-14 isotopes is the first method used in archaeological and geological studies to discriminate effective biological components. Applying the Carbon-14 method to the detection of a mixed combustion power plant of biomass and coal is different from applying it to the detection of a waste incineration power plant, and the supply of biomass fuel is affected by seasonal changes and collection radius. In China, it may be difficult for mixed combustion power plants to have a biomass content of more than 5%. At low compounding ratios, Accelerator Mass Spectrometry is the most accurate method for detecting carbon-14 abundance, and the sample must first be converted to graphite before testing.

In the prior art, the entire carbon-14 abundance measurement process had to be done separately in the mixed combustion power plant and in the laboratory, specifically the collection step was completed in the mixed combustion power plant and absorbed alkali. The agent is used to collect the carbon dioxide in the smoke gas, whereas the sample preparation step is completed in a specialized carbon-14 laboratory and receives the sample taken from the mixed combustion power plant. After that, a sample is prepared in a pipe in a high vacuum environment in the laboratory (preparation of a graphite sample), and then a computer test is performed to obtain data on the abundance of carbon-14. Not only is this sampling and preparation process time consuming, but it is inevitable that the collected carbon dioxide will be contaminated by atmospheric carbon dioxide during the storage period before and after it is collected by the alkaline absorber. The test results for the abundance of carbon-14 in the flue gas sample will be offset.

The present invention has been submitted for the above-mentioned problems, and an object of the present invention is to simplify and speed up sampling and preparation, and to improve the accuracy of test results.

In order to achieve the above object of the invention, the present invention has a sample tube for storing a smoke gas sample, CO ₂ and CO in the smoke gas sample are reduced to graphite in the sample tube, and the sample tube is in the smoke gas. It is a graphitization device provided with an intake port for introducing a sample into a sample tube and an exhaust port for discharging a smoke gas sample from the sample tube. Gas cleaning and sample collection can be realized by opening and closing the intake port and the exhaust port, and the sample can be sampled. A graphitizer is provided in which CO ₂ and CO in the smoke gas sample stored in the tube are finally converted into graphite under a positive pressure environment.

In this technical proposal, the graphitization device can directly introduce a flue gas sample to prepare a sample, and can also perform gas cleaning and sampling by combining the installation and opening / closing of an intake port and an exhaust port, and is correct. Samples can be prepared under pressure environment. Specifically, when both the intake and exhaust ports are open, the smoke gas sample is introduced from the intake port and the sample tube can be gas-cleaned, with air and other impurity gas components in the gas-cleaned sample tube. Is eliminated, the effect of modern carbon on the graphite sample is reduced, and after gas cleaning is complete, the intake and exhaust ports are closed to complete the sampling of the smoke gas sample.

The technical proposal provided by the present invention realizes the integration of sampling and preparation of a flue gas sample. Unlike conventional technical proposals, the technical proposal provided by the present invention does not require the storage of an alkali absorber to collect CO ₂ in flue gas, but is collected by the power plant in the conventional technical proposal. It solves the problem that the CO ₂ sample is easily contaminated during the storage and transfer process, and improves the accuracy of the detection result of the abundance of carbon-14 in the flue gas sample. The technical proposal provided by the present invention no longer relies on the high vacuum pump unit required by the conventional technical proposal, has a simple structure, and reduces the manufacturing cost of the sampling / preparation system.

In the preferred technical proposal of the present invention, a drug tube for accommodating the drug powder required for catalytic reduction of CO is provided inside the sample tube. In the preferred technical proposal of the present invention, the sample tube includes an upper sample tube provided with a cold trap for capturing the water vapor generated by the reduction reaction, a middle sample tube provided with a drug tube inside, and CO ₂ Includes a lower sample tube for accommodating the drug powder required for catalytic reduction of the above, in which the upper sample tube and the lower sample tube are connected to the upper and lower ends of the middle sample tube and can be freely removed. It is replaceable.

In this technical proposal, the upper sample tube is connected to the upper end of the middle sample tube and can be freely removed and replaced so that the cleaning of the sample tube and the removal and replacement of the drug tube in the middle sample tube are convenient. be. The lower sample tube is connected to the lower end of the middle sample tube and can be freely removed and replaced so that the lower sample tube can be conveniently cleaned, removed and replaced. As a whole, the upper, middle, and lower sample tubes are separated and connected, and the removal, replacement, and installation of the sample tubes are very quick and convenient.

In the preferred technical proposal of the present invention, the drug contained in the lower sample tube can be selected from a mixed powder of Zn powder and TiH ₂ , and TiH ₂ provides H ₂ and is in the sample tube under the catalytic action of Zn. Used to convert CO ₂ in CO to CO.

In the preferred technical proposal of the present invention, Fe powder can be selected as the drug contained in the drug tube of the sample tube in the middle stage, and CO in the sample tube is converted to graphite carbon alone under the catalytic action of Fe.

The preferred technical proposal of the present invention further includes a temperature control device that surrounds the sample tube, and the temperature control device is installed so as to surround the upper sample tube, the middle sample tube, and the lower sample tube, respectively. It is equipped with an upper temperature control device, a middle temperature control device, and a lower temperature control device that can independently control the temperature.

In this technical proposal, the temperature control device indirectly controls the temperature of the sample tube covered therein by adjusting its own temperature, and provides temperature conditions for the reduction reaction of CO ₂ and CO. The smoke gas sample undergoes a reduction reaction in the sample tube to produce graphite. The upper temperature control device, the middle temperature control device, and the lower temperature control device can control the temperature independently, and can provide appropriate temperature conditions according to the needs of different parts of the sample tube.

The preferred technical proposal of the present invention further includes a temperature control device in which a plurality of grooves for independently controlling the temperature are formed, and a plurality of sample tubes are formed and each of them is accommodated in each groove.

In this technical proposal, multiple tanks having the function of independently controlling the temperature are installed according to multiple sample tubes, and multiple smoke gas samples can be collected at the same time zone for sampling and preparation. On the other hand, it is possible to collect smoke gas samples at different times and realize continuous sampling and preparation for a long time.

The present invention is further one of a collection pipe for collecting a flue gas sample generated in a mixed combustion power plant and one of the above technical proposals connected to the collection pipe and capable of converting CO ₂ and CO in the flue gas sample into graphite. Flue gas sample purification that is connected between the graphitizer and the collection pipe and the flue gas sample and can filter out one or more of the particulate matter, corrosive gas, and steam in the flue gas sample. An instrument and a sampling and preparation system including are provided.

In this technical proposal, the smoke gas sample is purified by the smoke gas sample purification device, and then the concentration of harmful impurity gas sent into the graphitization device is reduced, the graphite conversion rate of the smoke gas sample is increased, and carbon is used. The detection error of the abundance of -14 is further reduced.

The sampling / preparation system of the present invention provides an integrated solution as compared with the conventional technical proposal in which the sampling stage and the sample preparation stage have a large time and space division. That is, since all the sampling and preparation are performed in the graphitizer, the time cost is greatly saved. In addition, the smoke gas sample is directly graphitized under positive pressure, no longer depends on the high vacuum pump unit required in the conventional technical proposal, the structure is simple, and the manufacturing cost of the sampling / preparation system is reduced. Further, miniaturization and portability of the sampling / preparation system in this field will be realized. In the technical proposal provided by the present invention, it is not necessary to store the alkaline absorber to collect CO ₂ in the flue gas, and the CO ₂ sample collected by the power plant in the conventional technical proposal can be stored. It solves the problem of being easily contaminated during the transfer process and improves the accuracy of the detection result of carbon-14 abundance in flue gas samples.

In a preferred technical proposal of the sampling / preparation system of the present invention, a smoke gas sample analyzer connected to a smoke gas sample purification device for measuring the concentration of CO ₂ and CO in the purified smoke gas sample is further provided. include.

In this proposal, by installing a smoke gas sample analyzer, the concentrations of CO ₂ and CO in the smoke gas sample can be obtained, and the carbon element in the smoke gas can be used to calculate the conversion efficiency to graphite. The CO ₂ and CO concentrations in the smoke gas sample can also be used as a reference for the initial placement amount and exchange amount of the chemicals in the graphitizer, and the deterioration of the graphite conversion efficiency due to insufficient or excessive chemical amounts can be avoided.

In a preferred technical proposal of the present invention, the smoke gas sample purifier comprises a front dust filter for filtering particulate matter in the smoke gas sample and a corrosive gas trap for collecting the corrosive gas in the smoke gas sample. It includes a collector, a dryer for removing water vapor in the smoke gas sample, and a rear dust filter for further filtering particulate matter in the smoke gas sample.

In this proposal, the smoke gas sample purifier can filter out one or more of the particulate matter, corrosive gas, and steam in the smoke gas sample, and the collection pipe is generated at the mixed combustion power plant. After collecting the smoke gas sample and purifying the smoke gas sample by the smoke gas sample purification device, most of the impurity gas having an inhibitory effect on the reduction reaction is removed, and CO ₂ and CO are sent into the graphitization device. The gas concentration of carbon-14 is increased, the graphite conversion rate of the reduction reaction is increased, and the detection error of the abundance of carbon-14 is further reduced.

The present invention further provides a sampling / preparation method, which is a sampling / preparation method applied to the above-mentioned sampling / preparation system.
A collection step to collect flue gas samples generated at a mixed combustion power plant,
A smoke gas sample purification step that filters out and removes one or more of the particulate matter, water, and corrosive gas in the smoke gas sample collected in the collection step.
It includes a sample collection / preparation step of reducing CO ₂ and CO in the smoke gas sample purified in the smoke gas sample purification step to graphite.

Compared to the prior art of collecting CO ₂ in smoke gas alone using an alkali absorber, the object collected in the collection step of the present invention is a smoke gas sample and is therefore provided by the present invention. The collection step of the sampling / preparation method is simpler and easier to realize, and in the sampling / preparation step, the present invention directly converts the carbon element in the smoke gas sample after purification into graphite. Therefore, the process of collecting and re-releasing CO ₂ in the conventional technique is omitted, and not only is it simpler, but also the problem that the CO ₂ sample is easily contaminated during the process of storage and transfer is avoided. The accuracy of the detection result of carbon-14 abundance in the smoke gas sample is improved.

Here, in order to distinguish the steps of each stage, "sampling" refers to collecting a smoke gas sample purified by a graphitizer, and "sample preparation" means collecting a smoke gas sample. Refers to preparing a graphite sample by a reduction reaction with a graphitizer.

In the preferred technical proposal of the present invention, after the flue gas sample purification step, and before the sampling / preparation step, further
A smoke gas sample analysis step to measure the CO ₂ and CO concentrations in the purified smoke gas sample, and
It is provided with an adjustment step for adjusting the amount of the drug used in the sample preparation step according to the measurement result of the flue gas sample analysis step.

In this proposal, the CO ₂ and CO concentrations in the smoke gas sample can be obtained and used to calculate the graphitization efficiency in the graphitizer, while the CO ₂ and CO concentrations in the graphitization device are graphitized. It can also be used as a reference for the initial placement amount and replacement amount of the drug in the process, and it is possible to avoid a decrease in graphite conversion efficiency due to insufficient or excessive amount of the drug.

According to the present invention, the compounding ratio of biomass can be calculated by quickly and accurately measuring the abundance of carbon-14 in the smoke gas sample of the mixed combustion power plant.

It is a principle schematic diagram of the Example of this invention. It is a structural schematic diagram of the graphitization apparatus of the Example of this invention. It is a structural schematic diagram of the flue gas sample purification apparatus in FIG. It is a flowchart of the sampling and preparation method of the Example of this invention. It is a flowchart of another sampling and preparation method of an Example of this invention.

Hereinafter, the technical proposal in the examples of the present invention will be described clearly and completely in accordance with the drawings in the embodiments of the present invention, but the described examples are only a part of the embodiments of the present invention and are all described. It is clear that this is not an example of. Based on the examples in the present invention, all other examples obtained by those skilled in the art without creative labor belong to the scope of protection of the present invention.

(Overall configuration of sampling / preparation system)
Explaining with reference to FIG. 1-3, the sampling / preparation system provided by the present embodiment is mainly described.
A collection pipe 1 for collecting the smoke gas sample generated in the mixed combustion power plant, a graphitization device 2 connected to the collection pipe 1 and capable of converting CO ₂ and CO in the smoke gas sample into graphite, and a collection pipe 1. A smoke gas sample purification device 3 and a smoke gas sample purification device which are connected to the graphitization device 2 and can filter and remove one or more of particulate matter, corrosive gas, and steam in the smoke gas sample. A smoke gas sample analyzer 4 connected to 3 and capable of measuring the concentrations of CO ₂ and CO in the purified smoke gas sample, and an air extraction device 5 for providing power for the smoke gas sample to flow in the system piping. And, including.

The collection pipe 1 is connected to the smoke gas channel of the boiler of the mixed combustion power plant, and the smoke gas is introduced into the collection pipe 1 through an opening installed in the smoke gas channel.

The smoke gas sample purification device 3 is connected to the collection pipe 1 and can filter out one or more of particulate matter, corrosive gas, and steam in the smoke gas sample, and the smoke gas sample is a smoke gas sample. After purification by the purification device 3, most of the impurity gas having an inhibitory effect on the reduction reaction is removed, the gas concentrations of CO ₂ and CO sent into the graphitization device 2 are increased, and the graphite conversion rate of the reduction reaction is increased. In particular, as shown in FIG. 3, the smoke gas sample purification device 3 includes a front dust removing filter 31, a corrosive gas collector 32, a dryer 33, and a rear dust removing filter 34. include. The front dust filter 31 is used to filter particulate matter in the smoke gas sample, the corrosive gas collector 32 is used to collect the corrosive gas in the smoke gas sample, and the dryer 33 is smoke. Used to remove water vapor in the gas sample, the rear dust filter 34 is used to further filter the particulate matter in the smoke gas sample. Among them, the rear dust filter 34 can adopt a HEPA filter screen in order to improve the filtration effect. Of course, the flue gas sample purification device 3 may selectively include one or more of the front dust filter, the corrosive gas collector, the dryer, and the rear dust filter.

The graphitization device 2 is connected to the smoke gas sample purification device 3, and after the particulate matter and the impurity gas are removed from the smoke gas sample collected by the collection pipe 1, CO ₂ and CO in the smoke gas sample are graphite. The specific configuration and operation steps of the graphitizer 2, which is converted to graphite in the atomizer 2, will be described in detail below.

The smoke gas sample analyzer 4 is installed between the smoke gas sample purification device 3 and the graphitization device 2, and can measure the concentrations of CO ₂ and CO in the smoke gas sample after purification. The structure of the smoke gas sample analyzer 4 is not particularly limited, and a conventional smoke gas analyzer and a mass flow controller can be adopted. Note that the smoke gas sample analyzer 4 may be installed downstream of the graphitizer 2, that is, between the graphitizer 2 and the bleed air device 5, depending on different needs. The smoke gas sample analyzer 4 is connected between the smoke gas sample purification device 3 and the graphitization device 2 by a bypass method.

The bleeding device 5 is connected to the graphitizing device 2 and is used to provide power for the flue gas sample to flow in the system piping, and its structure is not particularly limited.

Compared with the conventional separable sampling / preparation system, in the sampling / preparation system provided by this embodiment, all the sampling / preparation is performed in the graphitizer 2, and the sampling / preparation is performed. Higher efficiency. Further, in order to realize sample preparation in a positive pressure environment, it is not necessary to directly introduce a smoke gas sample into the graphitization device 2 to perform gas cleaning and install a vacuum pump unit that provides vacuum conditions. Will be simplified and the sampling and preparation system will be miniaturized. Since the step of collecting and storing CO ₂ in the flue gas sample is omitted, the problem that the collected CO ₂ is easily contaminated during the storage process is solved, and carbon-14 in the flue gas sample is used. The abundance measurement results are guaranteed to be more accurate.

(Control method of sampling / preparation system)
Based on the above aspects, the present invention further provides a sampling / preparation method, which is collected in a collection step and a collection step for collecting a smoke gas sample produced in a mixed combustion power plant, as shown in FIG. The smoke gas sample purification step of filtering and removing one or more of particulate matter, water, and corrosive gas in the smoke gas sample, and CO ₂ and CO in the smoke gas sample purified in the smoke gas sample purification step. , Includes sampling and preparation steps to reduce to graphite.

In the collection step, the flue gas sample produced at the mixed combustion power plant is introduced into the collection pipe 1 through an opening installed in the flue gas channel and uses an alkaline absorber to capture CO ₂ in the flue gas alone. The sampling step is simpler and easier to realize because the object to be sampled in the sampling step in this embodiment is a smoke gas sample as compared with the conventional technique for collecting.

In the smoke gas sample purification step, the smoke gas sample purification apparatus 3 filters and removes one or more of the particulate matter, water, and corrosive gas in the smoke gas sample.

In the sampling / preparation step, the graphitizer 2 reduces CO ₂ and CO in the smoke gas sample purified in the smoke gas sample purification step to graphite. In this embodiment, since the carbon element in the flue gas sample after purification is directly converted into graphite, the process of collecting and re-releasing CO ₂ in the conventional technical proposal is omitted, and it is only simpler. Instead, the problem that the CO ₂ sample is easily contaminated during the storage and transfer process is avoided, and the accuracy of the carbon-14 abundance detection result in the flue gas sample is improved.

The graphite sample obtained in the sampling / preparation step is taken out, transported to a mass spectrum analyzer for measurement, and the abundance of carbon-14 is obtained. Further, the mixing ratio of biomass can be calculated by using the abundance of carbon-14 in the flue gas according to the amount of the flue gas. The mass spectrum analyzer is not particularly limited, and an accelerator mass spectrometer is preferably used.

Preferably, as shown in FIG. 5, the concentrations of CO ₂ and CO in the smoke gas sample after the smoke gas sample purification step, before the sample preparation step, and further after purification by the smoke gas sample analyzer 4 are measured. It includes a smoke gas sample analysis step to be measured and an adjustment step for adjusting the amount of the drug used in the sample collection / preparation step according to the measurement result of the smoke gas sample analysis step. While the CO 2 and CO concentrations in the smoke gas sample can be used to obtain the CO ₂ and CO concentrations and be used to calculate the graphitization efficiency in the graphitizer, the CO ₂ and CO concentrations in the graphitizer sample are those of the chemicals during the graphitization process. It can also be used as a reference for the initial placement amount and replacement amount, and it is possible to avoid a decrease in graphite conversion efficiency due to insufficient or excessive amount of chemicals. The execution subject of the adjustment step is not particularly limited, and can be performed by the control unit communicatively connected to the graphitizing device 2, and the installation position of the control unit is not particularly limited. The adjustment method in the adjustment step is not particularly limited, and for example, the amount of the reducing substance can be adjusted in conjunction with the drug supply mechanism.

(Overall configuration of graphitizer 2)
Hereinafter, the overall configuration of the graphitizer 2 will be described.

As shown in FIG. 2, the graphitizing device 2 mainly includes a sample tube 21 and a temperature control device 22 covered with the outside of the sample tube 21.

The sample tube 21 includes a sample tube 212 in the middle stage, an upper sample tube 211 and a sample tube 213 in the lower stage, which are connected to the upper and lower ends of the sample tube 212 in the middle stage and can be freely removed and replaced.

The main body material of the sample tube 21 must not react with the flue gas sample or H2 at a _high temperature, and an inert metal having good ductility or a glass material which is easy to be produced at low cost can be selected and used. The sample tube 21 may be a rectangular parallelepiped or a cylinder, and the sample tube 21 that adopts the rectangular parallelepiped or the cylinder is more convenient to remove and attach.

The upper sample tube 211 can be used as a cold trap to capture the water vapor generated in the process of graphitization of the smoke gas, and the inside of the middle sample tube 212 is a chemical powder necessary for catalytic reduction of CO (this implementation). In the form, a freely removable and replaceable drug tube 214 is provided for accommodating (preferably Fe powder), and repeated use of the drug tube 214 is not recommended in consideration of the memory effect of the drug tube 214. A glass material can be used to reduce the cost of use, and the lower sample tube 213 accommodates the chemical powder required for catalytic reduction of CO ₂ (in this embodiment, a mixed powder of TiH ₂ and Zn is preferable). Used for.

The upper sample tube 211 is connected to the upper end of the middle sample tube 212 and can be freely removed and replaced so that the cleaning of the sample tube 21 and the removal and replacement of the drug tube 214 are convenient. The lower sample tube 213 is connected to the middle sample tube 212 and can be freely removed and replaced so that the lower sample tube 213 can be conveniently cleaned, removed and replaced. The separated sample tubes 21 can be sealed by screw connection at the time of assembly, whereby the sealing effect after combining the sample tubes is enhanced. As long as CO ₂ and CO in the flue gas sample can be efficiently catalytically reduced to graphite, the chemicals in the chemical tube 214 and the lower sample tube 213 are not particularly limited.

The sample tube 212 in the middle stage is provided with an intake port 2121 and an exhaust port 2122. The intake port 2121 is communicated with the collection pipe 1 so that the smoke gas sample can enter the sample tube 212 in the middle stage, and the exhaust port 2122 discharges the smoke gas sample from the sample tube 212 in the middle stage. The intake port 2121 can communicate with the collection pipe 1 using the pipe in which the valve 2123 is installed, and the exhaust port 2122 can discharge the gas introduced into the sample pipe 21 using the pipe in which the valve 2124 is installed. .. By controlling the opening and closing of the valve 2123 and the valve 2124 on the pipe, sampling and gas cleaning of the graphitizer 2 can be realized.

The temperature control device 22 includes a temperature control device 221 in the upper stage, a temperature control device 222 in the middle stage, and a temperature control device 223 in the lower stage.

Each of the sample tubes 21 corresponds to the temperature control device 22, that is, the upper temperature control device 221 is covered with the outside of the upper sample tube 211, and the middle temperature control device 222 is covered with the outside of the middle sample tube 212. The lower temperature control device 223 is covered with the outside of the lower sample tube 213. The temperature control systems of the upper temperature control device 221, the middle temperature control device 222, and the lower temperature control device 223 are independent of each other. The temperature control device 222 in the middle stage and the temperature control device 223 in the lower stage can select and use a resistance furnace that can be programmed and adjusted so as to provide the variable high temperature required for the graphitization reaction. The upper temperature control device 221 can use the semiconductor refrigeration chip so that the upper sample tube 211 provides the low temperature stage necessary for collecting the water vapor generated during the graphitization reaction of the smoke gas sample.

Preferably, the temperature control device for the sample tube 21 is not limited to the above embodiment, and may be formed so as to have a plurality of columns that independently control the temperature. The sample tube 21 is formed in a plurality and each groove. Is housed in.

In this technical proposal, a plurality of tanks having a function of independently controlling the temperature are installed in accordance with a plurality of sample tubes 21, and a plurality of smoke gas samples are collected at the same time zone for sampling and preparation. On the other hand, it is possible to collect smoke gas samples at different times and realize continuous sampling and preparation for a long time.

The sample tube 21 is used to store the smoke gas sample, CO ₂ and CO in the smoke gas sample are reduced to graphite in the sample tube 21, and the temperature control device 22 is a sample covered inside the sample tube 21. The temperature of the tube 21 is indirectly controlled by adjusting its own temperature, and provides temperature conditions for the reduction reaction of CO ₂ and CO.

Preferably, a sensor 23 may be further provided in the sample tube 21, the wire of the sensor 23 is connected to an external terminal via an air hole, and the sensor 23 is a pressure sensor, a temperature sensor, and a humidity sensor. The sensor 23 can better monitor the pressure, temperature, or humidity in the sample tube 21, and more conveniently monitor and control the progress of the graphitization reaction.

(Step of using graphitizer 2)
Hereinafter, the steps for using the graphitizer 2 will be described.

An appropriate amount of TiH ₂ and Zn mixed powder is placed in the lower sample tube 213, an appropriate amount of Fe powder is placed in the drug tube 214 in the middle sample tube 212, the upper sample tube 211, the middle sample tube 212, and the lower stage. After the sample tube 213 of the above is firmly connected, a closed environment is formed in the sample tube 21, a temperature control device 22 is attached, and the temperature of the middle stage temperature control device 222 and the lower stage temperature control device 223 is raised to 300 ° C. A preparation step to raise and maintain for 1 hour.

After the temperature inside the sample tube 21 has been cooled to the environmental level, the intake port 2121-sample tube 21-exhaust port 2122 is held so as to be open, a smoke gas sample is introduced, and the sample tube 21 is smoked at a constant gas flow rate. After washing with the gas sample for a certain period of time, the sample tube 21 was formed into a closed environment in the above preparation step. Therefore, when the valve 2123 and the valve 2124 were opened, the smoke gas sample was discharged from the intake port 2121 through the pipe in the middle stage. It can enter the sample tube 212 and further diffuse to the rest of the sample tube 21, and the smoke gas sample is discharged from the sample tube 21 to the collector or air connected to the exhaust port 2122 via the exhaust port 2122 and gas. The cleaning time is a gas cleaning step controlled by closing valves 2123 and 2124.

After the gas cleaning step, the sampling step of closing the valve 2123 and the valve 2124 to seal the smoke gas sample in the sample tube 21.

By raising the temperature of the sample tube 212 in the middle stage and the sample tube 213 in the lower stage to 500 ° C. and maintaining it for 3 hours, and then raising the temperature to 550 ° C. and maintaining it for 4 hours, CO ₂ and CO in the sample tube 21 are gradually increased. A sample preparation step of collecting water vapor generated during the process of graphitization by reducing to graphite and maintaining the temperature of the upper sample tube 211 at −20 ° C. The graphite sample obtained in the sample preparation step is taken out from the sample tube 21 and sent to a mass spectrum analyzer for testing.

Hereinafter, the sample preparation step will be described in detail.
In the sample preparation step, the middle sample tube 212, the upper sample tube 211, and the lower sample tube 213 of the sample tube 21 have different functions.

The lower sample tube 213 is connected to the lower end of the middle sample tube 212 for convenient addition and replacement of TiH ₂ and Zn powder, and can be freely removed and replaced. The TiH ₂ powder in the sample tube 213 of the above is decomposed under high temperature conditions to produce H ₂ , and CO ₂ in the smoke gas sample is reduced to CO under the catalytic action of H ₂ and Zn.

The lower sample tube 213 is connected to the lower end of the middle sample tube 212 for convenient addition and replacement of TiH ₂ and Zn powder, and can be freely removed and replaced. The TiH ₂ powder in the sample tube 213 of the above is decomposed under high temperature conditions to produce H ₂ , and CO ₂ in the smoke gas sample is reduced to CO under the catalytic action of H ₂ and Zn.

The upper sample tube 211 is also freely removable and replaceable for convenient cleaning of the sample tube and removal and replacement of the drug tube 214, is connected to the upper end of the middle sample tube 212, and is a sample preparation step. CO ₂ and O ₂ in the smoke gas sample react with H ₂ to generate water vapor, suppress the graphitization reaction, and are generated during the reaction by maintaining the temperature of the upper sample tube 211 at -20 ° C. It can capture the water vapor that has been created.

The upper sample tube 211 is also freely removable and replaceable for convenient cleaning of the sample tube and removal and replacement of the drug tube 214, is connected to the upper end of the middle sample tube 212, and is a sample preparation step. CO ₂ and O ₂ in the smoke gas sample react with H ₂ to generate water vapor, suppress the graphitization reaction, and are generated during the reaction by maintaining the temperature of the upper sample tube 211 at -20 ° C. It can capture the water vapor that has been created.

The parameters such as temperature and time in each of the above steps are merely examples, and can be flexibly adjusted according to actual needs.

Preferably, the purity of the TiH ₂ powder is 99% or more, the purity of the Zn powder is 99.9% or more, and the purity of the Fe powder is 99.5% or more, so that the contamination contained in the chemical is reduced.

According to the present invention, the structure of the graphitizer is redesigned so that sampling and preparation are integrated, the sampling and preparation system is also redesigned in connection therewith, and a new sampling and preparation method is used. Is provided.

The above is merely a preferred embodiment of the present invention, not intended to limit the present invention, and any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention are all of the present invention. It shall be included in the protection range of.

1-Collecting pipe 2-Graterization device 21-Sample tube 211-Upper sample tube 212-Middle sample tube 2121-Intake port 2122-Exhaust port 2123-Valve 2124-Valve 213-Lower sample tube 214-Pharmaceutical tube 22 -Temperature control device 221-Upper stage temperature control device 222-Middle stage temperature control device 223-Lower stage temperature control device 23-Sensor 3-Smoke gas sample purification device 31-Front dust filter 32-Corrosive gas collector 33 -Dryer 34-Rear dust filter 4-Smoke gas sample analyzer 5-Extractor

Claims (10)

It has a sample tube for storing a smoke gas sample, and CO ₂ and CO in the smoke gas sample are reduced to graphite in the sample tube.
In the sample tube,
An intake port for introducing the flue gas sample into the sample tube,
An exhaust port for discharging the flue gas sample from the sample tube is provided.
A graphitization device characterized in that gas cleaning and sampling can be realized by opening and closing the intake port and the exhaust port, and a sample can be prepared in a positive pressure environment. The graphitizing apparatus according to claim 1, wherein a drug tube for accommodating a drug powder necessary for catalytic reduction of CO is provided inside the sample tube. The sample tube is
The upper sample tube provided with a cold trap for capturing the water vapor generated by the reduction reaction,
The sample tube in the middle stage where the drug tube is provided inside, and
Includes a lower sample tube for accommodating the drug powder required for catalytic reduction of CO ₂ .
The graphitization apparatus according to claim 2, wherein the upper sample tube and the lower sample tube are connected to both upper and lower ends of the middle sample tube and can be freely removed and replaced. Further including a temperature control device surrounding the sample tube, the temperature control device is installed so as to surround the upper sample tube, the middle sample tube, and the lower sample tube, respectively, and the temperature is independently set. The graphitization device according to any one of claims 1 to 3, further comprising a temperature control device in the upper stage, a temperature control device in the middle stage, and a temperature control device in the lower stage. One of claims 1 to 3, further comprising a temperature control device in which a plurality of grooves for independently controlling the temperature are formed, and the sample tubes are formed in a plurality of grooves and each of the sample tubes is accommodated in the grooves. The graphitizer according to the section. A collection pipe that collects flue gas samples generated at a mixed combustion power plant,
The graphitizing apparatus according to any one of claims 1 to 5, which is connected to the collection pipe and can convert CO ₂ and CO in the smoke gas sample into graphite.
A smoke gas sample purification device connected between the collection pipe and the graphitization device and capable of filtering out one or more of particulate matter, corrosive gas, and water vapor in the smoke gas sample. A sampling and preparation system characterized by inclusion. The sixth aspect of claim 6, further comprising a smoke gas sample analyzer connected to the smoke gas sample purification apparatus and for measuring the concentrations of CO ₂ and CO in the smoke gas sample after purification. Sampling and preparation system. The flue gas sample purification device is
A front dust filter for filtering particulate matter in flue gas samples,
A corrosive gas collector for collecting corrosive gas in flue gas samples,
A dryer for removing water vapor in flue gas samples,
The sampling / preparation system according to claim 6 or 7, further comprising a rear dust filter for further filtering particulate matter in a flue gas sample. A sampling / preparation method applied to the sampling / preparation system according to any one of claims 6 to 8.
A collection step to collect flue gas samples generated at a mixed combustion power plant,
A smoke gas sample purification step that filters out one or more of the particulate matter, water, and corrosive gas in the smoke gas sample.
A sample collection / preparation method comprising a sample collection / preparation step of reducing CO ₂ and CO in a smoke gas sample purified in the smoke gas sample purification step to graphite. After the flue gas sample purification step and before the sample preparation step, further
A smoke gas sample analysis step for measuring the concentrations of CO ₂ and CO in the smoke gas sample after purification, and a smoke gas sample analysis step.
The sample collection / preparation method according to claim 9, further comprising an adjustment step for adjusting the amount of the drug used in the sample collection / preparation step according to the measurement result of the smoke gas sample analysis step. ..

Images