A carbon fixation amount measuring device using the gas pressure quantitative method and a carbon fixation amount measuring method using the device.

Abstract

The present invention provides a carbon fixation amount measuring device using a gas pressure quantitative method that can eliminate gas pressure fluctuations caused by human factors, and a carbon fixation amount measuring method using the device. [Solution] By using a shaker, the reaction vessel 11 (main body 10) is shaken horizontally in a figure-eight trajectory at a constant speed, constant amplitude, and for a constant time, thus eliminating gas pressure fluctuations caused by human factors.

Description

Technical Field

[0004] , , , , , , , , , , , ,

[0001] The present invention relates to an apparatus for measuring the carbon fixation amount of a sample using a gas pressure quantification method and a measurement method thereof.

Background Art

[0002] [[ID=十一]] In recent years, in order to achieve a carbon-neutral society, the development of materials for absorbing and fixing carbon dioxide has been promoted. Therefore, there is a need for an apparatus and a method capable of quickly and simply measuring the amount (mass) of carbon fixed in the material. Here, the gas pressure quantification method is used for the quantitative evaluation of the carbon fixation amount. As an apparatus used for the gas pressure quantification method, for example, there is a calcium carbonate content test apparatus described in Non-Patent Document 1. This calcium carbonate content test apparatus determines the calcium carbonate content from the pressure of carbon dioxide gas generated when hydrochloric acid is added to calcium carbonate.

[0003] In the calcium carbonate content test apparatus (hereinafter referred to as "conventional measurement apparatus") described in Non-Patent Document No. 1, after calcium carbonate is put into the center of a cylindrical reaction vessel, a hydrochloric acid container containing hydrochloric acid is placed at the center of the bottom of the reaction vessel. Next, the reaction vessel is shaken to invert the hydrochloric acid container in the reaction vessel, thereby reacting calcium carbonate with hydrochloric acid. The pressure of carbon dioxide gas generated at this time (hereinafter referred to as "gas pressure") is measured by a pressure measurement device attached to the upper lid of the reaction vessel. The above operation is repeated to create a calibration curve based on the relationship between the mass of calcium carbonate and the generated gas pressure. [[ID=十八]]

Prior Art Documents

Patent Documents

[0004]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] In conventional measuring devices, the operator operates a cart on which the reaction vessel is placed, shaking the vessel horizontally on the cart to tip over the hydrochloric acid container inside. Using a cart reduces gas pressure fluctuations caused by the operator compared to the operator holding and shaking the reaction vessel with both hands. However, because the operator operates the cart, it was difficult to eliminate gas pressure fluctuations caused by human factors.

[0006] Furthermore, in conventional measuring devices, the sample (calcium carbonate) and hydrochloric acid are stirred by inverting a hydrochloric acid container inside the reaction vessel. Therefore, in order to eliminate any remaining reaction residue in the sample, that is, to react all of the sample adhering to the reaction vessel with the hydrochloric acid, it was necessary to add a larger amount of hydrochloric acid relative to the sample. Moreover, in conventional measuring devices, careful handling is required to avoid tipping the hydrochloric acid container when setting it at the bottom of the reaction vessel containing the sample, or when sealing the reaction vessel with a lid, which reduces the efficiency of the measurement work.

[0007] The present invention aims to provide a carbon fixation amount measuring device using a gas pressure quantitative method that can eliminate gas pressure fluctuations caused by human factors, and a carbon fixation amount measuring method using the device. [Means for solving the problem]

[0008] The carbon fixation amount measuring apparatus using the gas pressure quantitative method of the present invention is characterized by comprising a main body having a reaction vessel into which hydrochloric acid to be added to the sample is injected, a lid for sealing the reaction vessel, and a sample container into which the sample is placed, and a shaker for shaking the main body at a constant orbit and speed. The carbon fixation amount measurement method using the gas pressure quantitative method of the present invention is characterized by comprising the steps of: injecting hydrochloric acid into a reaction vessel; placing a sample into a sample container; holding the sample container on the lid with the opening of the sample container in close contact with the lower surface of the lid; setting the lid holding the sample container on the opening of the reaction vessel to seal the reaction vessel; setting the sealed reaction vessel on the shaking platform of a shaker; dropping the sample container inside the reaction vessel a certain distance and then rotating it 180 degrees to add the hydrochloric acid to the sample; and shaking the reaction vessel with the shaker at a constant trajectory and speed. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a carbon fixation amount measuring device using a gas pressure quantitative method that can eliminate gas pressure fluctuations caused by human factors, and a carbon fixation amount measuring method using the device. [Brief explanation of the drawing]

[0010] [Figure 1] This is an explanatory diagram of this embodiment, and is a front view of the carbon fixation amount measuring device. [Figure 2] This is an explanatory diagram of this embodiment, and is a cross-sectional view of the main body in a uniaxial plane. [Figure 3] This is an explanatory diagram of this embodiment, and is a cross-sectional view taken along another axial plane perpendicular to the cross-section in Figure 2. [Figure 4] This is an explanatory diagram of this embodiment, and is a plan view of the lid. [Figure 5] This is an explanatory diagram of this embodiment, showing a state in which the container is held in place by the lid after being attracted by a magnet. [Figure 6] This is an explanatory diagram of this embodiment, showing the state after the sample container has fallen from the state shown in Figure 5 and the bottom of the sample container has collided with the shaft. [Figure 7] This is an explanatory diagram of this embodiment, showing the state after the sample container has rotated 90 degrees from the state shown in Figure 6. [Figure 8] This is an explanatory diagram of this embodiment, showing the state after the sample container has rotated further by 180 degrees from the state shown in Figure 7. [Figure 9] This is an explanatory diagram of this embodiment, showing a calibration curve created based on the measurement results obtained by the carbon fixation amount measuring device. [Figure 10] This is an explanatory diagram of this embodiment, showing the relationship between the gas pressure of carbon dioxide produced when calcium carbonate and hydrochloric acid are reacted and the elapsed time. [Modes for carrying out the invention]

[0011] One embodiment of the present invention will be described with reference to the attached diagram. This section describes a carbon fixation amount measuring device 1 (hereinafter referred to as "measuring device 1") that uses calcium carbonate in which carbon dioxide has been absorbed and fixed as a sample, and measures the amount (mass) of carbon dioxide fixed in the sample using the gas pressure quantitative method.

[0012] As shown in Figure 1, the measuring device 1 comprises a main body 10 and a shaker 61 for shaking the main body 10. As shown in Figure 2 or Figure 3, the main body 10 comprises a reaction vessel 11 into which hydrochloric acid (not shown) is injected, a lid 31 that closes the reaction vessel 11, and a sample container 23 supported by a turning mechanism 41. The reaction vessel 11 comprises a cylindrical portion 12 whose centerline is vertically positioned ("up and down direction" in Figures 1 to 3), an annular opening 13 that forms the upper end of the reaction vessel 11, and a bottom portion 14 that forms the lower part of the reaction vessel 11.

[0013] The bottom surface 15 of the reaction vessel 11 (the upper surface of the bottom 14) has a circular flat portion 16 formed in the center of the bottom 14 of the reaction vessel 11 and an inclined portion 17 formed on the outer circumference of the flat portion 16. The flat portion 16 is positioned perpendicular to the centerline of the cylindrical portion 12, and its center intersects with the centerline of the cylindrical portion 12. The inclined portion 17 is inclined such that its height (distance upward) increases from the flat portion 16 in the radial direction of the cylindrical portion 12. In other words, the bottom surface 15 of the reaction vessel 11 is formed in the shape of an inner frustoconical (mortar-shaped) with an inner diameter that decreases downward.

[0014] The opening 13 of the reaction vessel 11 has a flange portion 19 that protrudes radially outward of the cylindrical portion 12. The flange portion 19 has a mating surface 18 parallel to a plane perpendicular to the center line of the cylindrical portion 12. An annular seal groove 21 for attaching an annular seal member 20 (an "O-ring" in this embodiment) is formed in the mating surface 18. The cylindrical portion 12, the opening 13, and the bottom portion 14 are made of a plastic material such as polyvinyl chloride.

[0015] The lid 31 is made of a disc-shaped acrylic plate. The lid 31 has a flange portion 34 that protrudes radially outward. A mating surface 35 that faces the mating surface 18 of the reaction vessel 11 is formed on the outer peripheral edge portion of the lid 31 including the flange portion 34. The mating surface 35 is pressed against and adheres to the seal member 20 attached to the opening 13 (seal groove 21) of the reaction vessel 11 when the lid 31 is attached to the opening 13 of the reaction vessel 11. Thereby, the inside of the reaction vessel 11 is sealed. The lid 31 has an instrument attachment hole 36 to which a pressure gauge 5 (see FIG. 1) for measuring the pressure inside the reaction vessel 11 is attached, and an instrument attachment hole 37 to which a thermometer 6 (see FIG. 1) for measuring the temperature inside the reaction vessel 11 is attached. For the sake of convenience, FIGS. 2 to 4 show a state in which the pressure gauge 5 and the thermometer in 6 are removed.

[0016] As shown in FIG. 5, the sample container 23 has a cylindrical portion 24 and a bottom portion 25. The sample container 23 has a metal washer 26 joined (adhered in this embodiment) to the end face on the opening side (the "upper side" in FIG. 5). The sample container 23 has a guide portion 27 that extends from the center of the bottom portion 25 to the side opposite to the opening side (the "lower side" in FIG. 5). The guide portion 27 is formed in a rectangular parallelepiped shape. The guide portion 27 has a guide hole 28 that extends from the bottom portion 25 along the center line of the cylindrical portion 24 to the side opposite to the opening side. The guide hole 28 penetrates the guide portion 27 in a direction perpendicular to the center line of the cylindrical portion 24 (the "left - right direction" in FIG. 2). The cylindrical portion 24, the bottom portion 25, and the guide portion 27 are made of a plastic material such as polyvinyl chloride.

[0017] As shown in FIG. 2 or FIG. 3, the turning mechanism 41 has a stay 42 formed in an L shape. The stay 42 has a fixing piece 44 fixed to the lower surface 33 of the lid body 31 by small screws 43, 43, and a support piece 45 extending perpendicular (in the "downward direction" in FIG. 2) to the lower surface 33 of the lid body 31. The turning mechanism 41 has a shaft 46 supported in a cantilever manner by the support piece 45 of the stay 42.

[0018] For convenience, the state where the lid body 31 is attached to the opening 13 of the reaction vessel 11 will be described. The shaft 46 is arranged such that its axis is orthogonal to the center line of the cylindrical portion 12 of the reaction vessel 11 (hereinafter referred to as the "center line of the reaction vessel 11"). As shown in FIG. 5, the shaft 46 is inserted into a guide hole 28 formed in the guide portion 27 of the sample container 23. The sample container 23 is movable in the direction along the center line of the reaction vessel 11 (vertical direction) and rotatable about the shaft 46 with the shaft 46 inserted into the guide hole 28.

[0019] The sample container 23 is held at the upper end holding position (see FIG. 5) by the washer 26 being attracted by the magnetic force of a disc-shaped magnet 47 (rare earth magnet) arranged on the upper surface 32 side of the lid body 31. The sample container 23 has the washer 26 abutted (adhered) against the lower surface 33 of the lid body 31 with the washer 26 attracted to the magnet 47. The sample container 23 is arranged at the holding position such that the center line of the cylindrical portion 24 substantially coincides with the center line of the reaction vessel 11. A cocoon-shaped recess 38 (see FIG. 4) for fitting and positioning the magnet 47 with a clearance is formed at the center of the upper surface 32 of the lid body 31. In this embodiment, a tool 49 in which two round bars 48 having magnets 47 (see FIG. 5) fixed to one end surface by bolts (not shown) are bundled in parallel is used.

[0020] When the magnet 47 separates from the recess 38 of the lid 31, the sample container 23 falls from its holding position (see Figure 5) due to its own weight. As the sample container 23 falls, the guide hole 28 is guided by the shaft 46. Then, when the bottom 25 of the sample container 23 collides with the shaft 46 (see Figure 6), the rebound causes it to rotate 180 degrees around the shaft 46, as shown in Figure 7. At this time, the rotation mechanism 41 restricts excessive rotation of the sample container 23 (rotation exceeding 180 degrees) by a stopper 50 attached to the lid 31.

[0021] The stopper 50 has an L-shaped stainless steel plate 51. The plate 51 has a fixing piece 52 that is fixed to the lower surface 33 of the lid 31 and a receiving piece 53 that extends perpendicularly (downward in Figure 3) to the lower surface 33 of the lid 31. A rubber plate 54 is attached (bonded) to the receiving surface of the receiving piece 53 to mitigate the impact when the sample container 23 collides with it. Note that the shaker 61 is an existing shaker in which the shaking platform 62 moves horizontally in a figure-eight trajectory, so a detailed description of the shaker 61 is omitted.

[0022] Next, we will explain how to measure the amount (mass) of carbon dioxide fixed in a sample (in this embodiment, "calcium carbonate that has absorbed and fixed carbon dioxide") using the measuring device 1. First, hydrochloric acid is poured into the reaction vessel 11. Meanwhile, a predetermined amount (mass) of sample is placed in the sample container 23, and the shaft 46 attached to the lid 31 is inserted through the guide hole 28 of the guide portion 27 of the sample container 23. Next, with the opening of the sample container 23 facing upwards, the washer 26 of the sample container 23 is pressed tightly against the lower surface 33 of the lid 31. As a result, the sample container 23 is closed by the lid 31.

[0023] In this state, the magnet 47 fitted into the recess 38 of the lid 31 attracts the washer 26 of the sample container 23, and holds the sample container 23 to the lid 31. Next, the lid 31 holding the sample container 23 is set into the opening 13 of the reaction vessel 11, and the fastening tool 3 is attached to the outer circumference of the flange portion 19 of the reaction vessel 11 and the flange portion 34 of the lid 31. Then, by tightening the fastening tool 3, the sealing member 20 is compressed between the mating surface 18 of the reaction vessel 11 and the mating surface 35 of the lid 31, and the reaction vessel 11 is sealed.

[0024] Next, the main body 10, with the reaction vessel 11 sealed by the lid 31, is placed on the shaking platform 62 of the shaker 61, and the magnet 47 is separated from the recess 38 of the lid 31. As a result, the sample container 23 falls from its holding position (see Figure 5) toward the bottom 14 of the reaction vessel 11 due to its own weight. When the bottom 25 of the sample container 23 collides with the shaft 46 (see Figure 6), the rebound causes the sample container 23 to rotate 180 degrees around the shaft 46 (see Figure 7). At this time, the sample container 23 is prevented from rotating excessively (rotating more than 180 degrees) by the stopper 50 attached to the lid 31 (see Figure 8).

[0025] The sample container 23 is rotated 180 degrees, and the opening of the sample container 23 faces downwards (upside down), allowing hydrochloric acid to be added to the sample, causing the sample (calcium carbonate) to react with the hydrochloric acid. Meanwhile, at the moment the magnet 47 is separated from the recess 38 of the lid 31, the shaker 61 is activated, and the reaction vessel 11 (main body 10) on the shaking platform 62 is moved horizontally in a figure-eight trajectory to shake. Thereafter, the gas pressure and temperature of carbon dioxide generated in the reaction vessel 11 are measured at regular intervals. This operation is repeated, and a calibration curve (see Figure 9) is created based on the relationship between the mass of the sample and the gas pressure.

[0026] Here, Figure 9 shows a calibration curve (hereinafter referred to as the "calibration curve") created based on the measurement results obtained by the measuring device 1 according to this embodiment, and a straight line (hereinafter referred to as the "theoretical line") drawn by the theoretical value of the gas pressure of carbon dioxide generated when calcium carbonate and hydrochloric acid react, on the same coordinate system. As shown in Figure 9, the measured values ​​represented by the calibration curve match the theoretical values ​​represented by the theoretical line. From this, it can be understood that by using the measuring device 1 according to this embodiment, the sample (calcium carbonate) and hydrochloric acid react completely in the reaction vessel 11, with no residue remaining, and all of the sample reacts with hydrochloric acid.

[0027] Figure 10 shows the relationship between gas pressure and elapsed time, obtained by repeatedly measuring the gas pressure of carbon dioxide generated when calcium carbonate reacts with hydrochloric acid without changing the mass of the sample (calcium carbonate). As shown in Figure 10, it can be seen that by using the measuring device 1 according to this embodiment, highly reproducible measurement results can be obtained even when repeatedly measuring carbon dioxide absorbed and fixed in the sample. Thus, by using the carbon fixation amount measuring device 1 using the gas pressure quantification method according to this embodiment and the carbon fixation amount measuring method using the measuring device 1, gas pressure fluctuations due to anthropogenic factors can be eliminated.

[0028] In conventional measuring devices, the operator manipulated a trolley on which the reaction vessel was mounted, causing the vessel to be shaken horizontally to react the sample (calcium carbonate) with hydrochloric acid inside. This made it difficult to eliminate gas pressure fluctuations caused by human factors in the gas pressure quantification method. In contrast, in this embodiment, a shaker 61 is used to shake the reaction vessel 11 (main body 10) horizontally in a figure-eight trajectory at a constant speed, constant amplitude, and constant time, thereby eliminating gas pressure fluctuations due to human factors in the gas pressure determination method. Furthermore, in conventional measuring devices, the hydrochloric acid container is inverted and rotated within the reaction vessel to agitate the sample and hydrochloric acid. Therefore, in order to eliminate any remaining reaction residue in the sample, it was necessary to add a larger amount of hydrochloric acid relative to the sample. In contrast, in this embodiment, the bottom surface 15 of the reaction vessel 11 is formed in the shape of an inner frustoconical (mortar-shaped), so that by adding a smaller amount of hydrochloric acid to the sample, the sample and hydrochloric acid can react without leaving any sample residue. Furthermore, with conventional measuring devices, careful handling is required to prevent the hydrochloric acid container from tipping over during preparation for measurement, such as when setting the hydrochloric acid container at the bottom of the reaction vessel containing the sample, or when sealing the reaction vessel with a lid. This has reduced the efficiency of the measurement process. In contrast, in this embodiment, a metal washer 26 attached to the opening end face of the sample container 23 is attracted by a magnet 47 from the outside of the reaction vessel 11 (the upper surface 32 side of the lid 31), thereby holding the sample container 23 containing the sample inside the reaction vessel 11. By separating the magnet 47 from the lid 31, the sample container 23 rotates 180 degrees inside the reaction vessel 11 and falls onto the bottom surface 15 of the reaction vessel 11, and the hydrochloric acid at the bottom 14 of the reaction vessel 11 is added to the sample. This makes it possible to avoid the sample container 23 tipping over at an unintended time, thereby improving the efficiency of the measurement work. Furthermore, in this embodiment, a stopper 50 is provided on the lower surface 33 of the lid 31 to restrict excessive rotation (rotation exceeding 180 degrees) of the sample container 23, thereby preventing the sample container 23 from swinging around the shaft 46 while suspended from it. Furthermore, in this embodiment, after the sample container 23 falls, it rotates on the shaft 46 and collides with the stopper 50. The impact of the collision causes all of the sample contained in the sample container 23 to fall from the sample container 23 into the hydrochloric acid in the reaction vessel 11.

[0029] The embodiments are not limited to the forms described above, and can be configured as follows, for example. In this embodiment, the turning mechanism 41 is configured to support the shaft 46 in a cantilever manner by the stay 42, but the turning mechanism 41 may also be configured to support the shaft 46 at both ends by a pair of stays 42, 42. In this case, the shaft 46 is inserted into the pair of stays 42, 42 in a removable manner. In this embodiment, a permanent magnet (rare earth magnet) is used for the magnet 47 that attracts the washer 26 of the sample container 23, but an electromagnet may also be used for the magnet 47. In this case, the magnet 47 can be fixed to the lid 31. By energizing the magnet 47 (electromagnet), the sample container 23 can be held in place by the lid 31, and by stopping the energization of the magnet 47, the sample container 23 can be dropped and rotated to add hydrochloric acid to the sample. In this embodiment, the shaker 61 was activated at the time the magnet 47 was separated from the recess 38 of the cover 31. However, the timing of activating the shaker may be before the magnet 47 is separated from the recess 38 of the cover 31. [Explanation of Symbols]

[0030] 1 Carbon fixation amount measuring device, 10 Main unit, 11 Reaction vessel, 23 Sample container, 31 Lid, 41 Rotation mechanism, 61 Shaker

Claims

1. A carbon fixation amount measuring device using the gas pressure quantitative method, A main body comprising a reaction vessel into which hydrochloric acid to be added to the sample is injected, a lid to seal the reaction vessel, and a sample container into which the sample is placed, A shaker that shakes the main body in a constant trajectory and at a constant speed, A carbon fixation amount measuring device using a gas pressure quantitative method, equipped with the necessary components.

2. A carbon fixation amount measuring device using the gas pressure quantitative method described in claim 1, The main body is a carbon fixation amount measuring device using a gas pressure quantitative method, which holds the sample container inside the reaction vessel and includes a turning mechanism that drops the sample container a certain distance from a state in which its opening is tightly sealed to the lid and then rotates it 180 degrees.

3. A carbon fixation amount measuring device using the gas pressure quantitative method described in claim 2, The turning mechanism includes a guide portion extending from the bottom of the sample container to the side opposite to the opening of the sample container, a guide hole formed in the guide portion and extending from the bottom of the sample container to the side opposite to the opening of the sample container, a shaft provided in the lid and positioned to extend horizontally inside the reaction vessel and inserted through the guide hole, and a holding means for holding the sample container with its opening in close contact with the lid. A carbon fixation amount measuring device using a gas pressure quantitative method, equipped with the necessary components.

4. A carbon fixation amount measuring device using the gas pressure quantitative method described in claim 3, The holding means includes a metal washer provided on the end face of the opening side of the sample container, and a magnet that attracts the washer from the upper surface side of the lid. A carbon fixation amount measuring device using a gas pressure quantitative method, equipped with the necessary components.

5. A carbon fixation amount measuring device using the gas pressure quantitative method described in claim 2 or 3, The aforementioned rotation mechanism is provided on the lower surface of the lid and includes a stopper that restricts the rotation of the sample container beyond 180 degrees, and is a carbon fixation amount measuring device using a gas pressure quantitative method.

6. A method for measuring the amount of carbon fixation using a carbon fixation amount measuring device using the gas pressure quantitative method described in claims 1 to 5, The steps include injecting hydrochloric acid into the reaction vessel, The steps include: placing the sample into the sample container, The steps include: holding the sample container on the lid with the opening of the sample container in close contact with the lower surface of the lid; The steps include: setting the lid holding the sample container onto the opening of the reaction vessel to seal the reaction vessel; The steps include setting the sealed reaction vessel on the shaking platform of the shaker, The step of dropping the sample container in the reaction vessel by a certain distance, then rotating it 180 degrees, and adding the hydrochloric acid to the sample, The steps include: shaking the reaction vessel with the shaker in a constant orbit and at a constant speed; A method for measuring carbon fixation using a gas pressure quantitative method, comprising the above.

Images