Sample acquisition apparatus, quality determination apparatus, and quality determination method

Abstract

To provide a sample acquisition apparatus configured to acquire a sample in a through hole of a catalyst for quality determination through highly accurate measurement without destroying the catalyst, a quality determination apparatus, and a quality determination method.SOLUTION: A sample acquisition apparatus 10 for acquiring a sample for quality determination from a through hole C1 of a catalyst C includes: a separation unit 11 which can separate a sample from an inner surface C1a of the through hole C1; a sampling tube 12 having one end where the separation unit 11 is disposed and allowing the sample separated by the separation unit 11 to flow therethrough; a suction unit 13 which can suck the inside of the sampling tube 12 from an opening at the other end side of the sampling tube 12; and a collection unit 14 which collects the sample sucked by the suction unit 13 via the sampling tube 12.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a sample acquisition device, a quality determination device, and a quality determination method.

Background Art

[0002] Conventionally, a catalyst having a honeycomb structure used for purifying exhaust gas is regenerated to recover its performance against performance degradation during use, and a technique for determining the quality of the catalyst after regeneration is known. Patent Document 1 is cited as an example of this type of technique. In Patent Document 1, it is described that the deterioration of the honeycomb catalyst is evaluated by measuring the thickness of the coating layer containing particles having a particle size of 2 μm or less deposited on the surface of the honeycomb catalyst.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] By the way, when determining the quality of a catalyst with higher precision using surface observation with a microscope or the like, component analysis, etc., in order to obtain a sample from inside the through-holes of the catalyst, it is necessary to destroy the catalyst, and it is not possible to inspect all of the catalysts, and there is a risk of overlooking poor quality of the catalyst.

[0005] An object of the present invention is to provide a sample acquisition device, a quality determination device, and a quality determination method capable of acquiring a sample inside the through-holes of a catalyst without destroying the catalyst for quality determination of the catalyst by high-precision measurement.

Means for Solving the Problems

[0006] (1) The sample acquisition device according to the present invention is a sample acquisition device that acquires a sample for quality determination from the through-hole of a catalyst, and includes a separation unit that can separate the sample from the inner surface of the through-hole, a collection tube having the separation unit disposed at one end thereof and through which the sample separated by the separation unit can flow, a suction unit that can suck the inside of the collection tube from an opening on the other end side of the collection tube, and a recovery unit that recovers the sample sucked through the collection tube by the suction unit.

[0007] (1) The sample acquisition device can acquire a sample in the through-hole of a catalyst for quality determination of the catalyst by high-precision measurement without destroying the catalyst.

[0008] (2) The sample acquisition device according to (1) further includes an imaging unit provided at one end side of the collection tube.

[0009] (2) The sample acquisition device can acquire a sample in the through-hole of a catalyst for quality determination of the catalyst efficiently without destroying the catalyst.

[0010] (3) In the sample acquisition device according to (1) or (2), the separation unit has a blade, and can separate the sample from the inner surface by cutting the inner surface with the blade.

[0011] (3) The sample acquisition device can acquire a sample in the through-hole of a catalyst for quality determination of the catalyst at a lower cost without destroying the catalyst.

[0012] (4) The quality determination device according to the present invention includes the sample acquisition device according to (1), an analysis unit that analyzes the sample recovered by the recovery unit, and a quality determination unit that determines the quality of the catalyst based on the component concentration derived from the analysis of the sample by the analysis unit.

[0013] (4) The quality determination device can efficiently determine the quality of a catalyst while acquiring a sample in the through-hole of the catalyst for quality determination of the catalyst without destroying the catalyst.

[0014] In the quality determination device described in (5)(4), the catalyst is a denitration catalyst, and the quality determination unit determines the quality of the catalyst based on the related information in which the component concentration of the sample and the denitration rate are associated.

[0015] The quality determination device of (5) can more efficiently determine the quality of the catalyst while obtaining a sample in the through-hole of the catalyst without destroying the catalyst for the quality determination of the catalyst by high-precision measurement.

[0016] In the quality determination device described in (6)(5), the analysis unit measures at least the component concentration of at least one of Ti, Al, and S in the catalyst by analysis, and the quality determination unit determines the quality of the catalyst based on the related information in which the component concentrations of Ti, Al, and S measured by the analysis of the analysis unit and the denitration rate are associated.

[0017] The quality determination device of (6) can more efficiently determine the quality of the catalyst while obtaining a sample in the through-hole of the catalyst without destroying the catalyst for the quality determination of the catalyst by high-precision measurement.

[0018] In the quality determination device described in (7)(6), when the pass determination criterion for the quality of the catalyst is that the denitration rate is 74.0% or more, the TiO of Ti measured by the analysis of the analysis unit 2 The component concentration in terms of conversion is 81.0% or more, and the Al of Al 2 O 3 The component concentration in terms of conversion is 1.5% or less, and the SO of S 3 When the component concentration in terms of conversion is 2.5% or less, the quality of the catalyst is determined to be qualified.

[0019] The quality determination device of (7) can more efficiently determine the quality of the catalyst while obtaining a sample in the through-hole of the catalyst without destroying the catalyst for the quality determination of the catalyst by high-precision measurement.

[0020] In the quality determination device described in at least any one of (8)(4) to (7), the analysis unit is an X-ray analyzer.

[0021] The quality determination device of (8) can determine the quality of the catalyst with higher precision while obtaining a sample in the through-hole of the catalyst without destroying the catalyst for quality determination of the catalyst by high-precision measurement.

[0022] (9) The quality determination method according to the present invention is the quality determination method of the catalyst using the sample acquisition device described in (1), and includes a separation step of separating the sample from the inner surface by the separation unit, a recovery step of recovering the sample separated in the separation step by the recovery unit, an analysis step of analyzing the components of the sample recovered in the recovery step, and a quality determination step of determining the quality of the catalyst based on the component concentration analyzed in the analysis step.

[0023] (9) The quality determination method can efficiently determine the quality of the catalyst while obtaining a sample in the through-hole of the catalyst without destroying the catalyst for quality determination of the catalyst by high-precision measurement.

Brief Description of the Drawings

[0024]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Embodiments for Carrying Out the Invention

[0025] <Quality Determination Device> Hereinafter, the quality determination device 1 according to an embodiment of the present invention will be described with reference to FIG. 1. The quality determination device 1 is a device for determining the quality of the honeycomb catalyst C as a catalyst. The quality determination device 1 according to the present embodiment determines the quality of the regenerated catalyst, but is not limited thereto. For example, the quality determination device may determine the quality of an unused catalyst for confirming the performance of the catalyst, or may determine the quality of the catalyst in use for considering the replacement timing of the catalyst. Examples of the form of the catalyst include known plate-shaped catalysts, lattice-shaped catalysts, corrugated catalysts, and the like. Any of the plate-shaped catalyst, lattice-shaped catalyst, and corrugated catalyst has through holes penetrating in the exhaust gas flow direction. In the present embodiment, the case where the honeycomb catalyst C is used as the lattice-shaped catalyst will be described. The honeycomb catalyst C is a catalyst having a honeycomb structure in which a plurality of through holes C1 are formed. The through hole C1 is also referred to as a cell, and is, for example, a small-diameter and long hole of 6 mm × 6 mm × 1000 mm.

[0026] The honeycomb catalyst C according to the present embodiment is a denitration catalyst used for purifying exhaust gas in a coal-fired power plant or the like. Examples of the denitration catalyst include those in which a catalyst component such as vanadium oxide is supported on a carrier such as TiO 2 etc. As the denitration catalyst is used for purifying exhaust gas, a coating layer having a thickness of about several micrometers with Si as a component is formed on the surface. When the coating layer is formed, the performance of the denitration catalyst deteriorates. Therefore, regeneration is performed to remove the silica layer formed on the surface of the denitration catalyst and restore the performance. The quality of the catalyst in this case indicates the denitration performance of the regenerated catalyst, and is indicated by, for example, the denitration rate. The catalyst is not limited to the denitration catalyst such as the honeycomb catalyst C according to the present embodiment, and is effective for catalysts that can be polished or the like. For example, the catalyst determined by the quality determination device may be a catalyst used for blast furnace gas or the like generated in a blast furnace of a steelworks, or a three-way catalyst for purifying automotive exhaust gas. Examples of the three-way catalyst include those in which a catalyst component of a noble metal such as Pt, Rh, and Pd is supported on a carrier such as ceramic. The quality of the catalyst in this case indicates the purification performance of the regenerated catalyst, and is indicated by, for example, the purification rate.

[0027] As shown in FIG. 1, the quality determination device 1 includes a sample acquisition device 10, an analysis unit 20, and an information processing device 30 having a quality determination unit 113 described later.

[0028] The sample acquisition device 10 is a device for acquiring a sample for quality determination from the through holes of the honeycomb catalyst C. As shown in FIG. 1, the sample acquisition device 10 includes a separation unit 11, a sampling tube 12, a suction unit 13, a recovery unit 14, and an imaging unit 15.

[0029] The separation unit 11 is configured to separate a sample from the inner surface C1a of the through hole C1. Specifically, the separation unit 11 is, for example, a blade. The inner surface C1a of the through hole C1 can be cut by the separation unit 11 to separate the sample from the inner surface C1a. The separation unit 11 is not limited to a blade. For example, the separation unit 11 may be a power tool or the like.

[0030] The sampling tube 12 is a tube through which the sample separated by the separation unit 11 can flow. One end side of the sampling tube 12 is fixed to the separation unit 11 and supports the separation unit 11. The separation unit 11 is fixed to the inner surface of the sampling tube 12, for example. More specifically, as shown in FIG. 2, a suction flow path IF for air sucked by the suction unit 13 is formed between the separation unit 11 and the sampling tube 12 at one end side of the sampling tube 12, and the separation unit 11 is fixed.

[0031] As shown in FIG. 3, the separation unit 11 is disposed at one end side of the sampling tube 12 such that the tip of the blade of the separation unit 11 is located inside the outer shape of the sampling tube 12 when viewed from one end side to the other end side of the sampling tube 12. With the above configuration, the shape protruding outside the sampling tube 12 is eliminated, so that the sampling tube 12 can be easily inserted without being caught in the through hole C1. The arrangement of the separation unit 11 on the sampling tube 12 is not limited to this.

[0032] The sampling tube 12 is long and preferably, for example, longer than the longitudinal length of the through-hole C1 of the honeycomb catalyst C. The outer diameter of the sampling tube 12 is smaller than the inner diameter of the through-hole C1 of the honeycomb catalyst C. Since the sampling tube 12 also serves as a structure for supporting the separation part 11 when cutting the inner surface C1a of the through-hole C1, it preferably has higher rigidity.

[0033] The sampling tube 12 does not necessarily have to also serve as a structure for supporting the separation part 11, and the sample acquisition device 10 may have a structure for separately supporting the separation part 11. In this case, the sampling tube 12 does not need to have high rigidity and may have flexibility.

[0034] The suction part 13 has a suction tube 13a and is configured to be able to suction the inside of the sampling tube from the opening on the other end side of the sampling tube 12 through the suction tube 13a. The suction part 13 suctions the inside of the sampling tube by a known configuration such as a fan.

[0035] The collection part 14 collects the sample suctioned through the sampling tube 12 by the suction part 13. The collection part 14 has, for example, a filter (not shown) and a container in which the sample trapped by the filter is accommodated. The configuration of the collection part 14 is not limited to this, and for example, the collection part 14 may have a cyclone for classifying the sample from the air suctioned by the suction part 13.

[0036] The imaging part 15 is configured to image the vicinity of the tip of the blade of the separation part 11 so that sampling can be performed while checking the video during sample sampling by the separation part 11. The imaging part 15 is, for example, a CCD camera. The configuration of the imaging part 15 is not limited to this. As shown in FIG. 3, the imaging part 15 is arranged at one end of the sampling tube 12 and at a position where the tip of the blade of the separation part 11 can be imaged. The imaging part 15 is connected to an information processing device 30 described later and has a cord (not shown) for receiving video information transmission and power supply of the imaging part 15. For convenience of explanation, the imaging part 15 is omitted in figures other than FIG. 3.

[0037] The analysis unit 20 is configured to analyze the sample collected by the sample acquisition device 10 for high-precision measurement. The analysis unit 20 includes a pipe 20a through which the sample collected by the collection unit 14 of the sample acquisition device 10 flows, and an analyzer 20b that analyzes the sample flowing through the pipe 20a. The analysis unit 20 is, for example, a known X-ray fluorescence (XRF) analyzer. The analysis unit 20 measures the concentration of at least one of the catalyst component, binder-ash component, and poisoning component from the sample collected at least from the honeycomb catalyst C by analysis. The analysis unit 20 according to the present embodiment measures the concentration of at least one of Ti, Al, and S from the sample collected at least from the honeycomb catalyst C by analysis and uses TiO 2 as the catalyst component, Al 2 O 3 as the binder-ash component, and SO 3 to derive the concentration of at least one of them. For example, the analysis unit 20 measures the component concentrations of Ti, Al, and S by analysis. The analysis unit 20 converts the measured component concentrations of Ti, Al, and S into the component concentrations of TiO 2 Al 2 O 3 and SO 3 respectively. When the honeycomb catalyst C is a three-way catalyst for an automobile, for example, the analysis unit 20 is configured to measure the concentration of at least one of Pt, Rh, and Pd as the catalyst component by analysis.

[0038] The configuration of the analysis unit 20 is not limited to the X-ray fluorescence analyzer. The method of moving the sample from the collection unit 14 to the analysis unit 20 is not limited to flowing through the pipe 20a. For example, it may be moved manually. The pretreatment required for analysis may be performed separately.

[0039] The information processing device 30 is configured to acquire the component concentration information analyzed by the analysis unit 20 and perform a process of determining the quality of the honeycomb catalyst C. An example of the hardware configuration of the information processing device 30 according to an embodiment of the present invention will be described with reference to FIG. 5. As shown in FIG. 5, the information processing device 30 includes a processor 100, a ROM (Read Only Memory) 101, a RAM (Random Access Memory) 102, a bus 103, an input / output interface 104, an input unit 105, an output unit 106, a storage unit 107, and a power supply 108.

[0040] The processor 100 is the central part of a computer that performs processes such as operations and controls necessary for the operation of the information processing device 30, and performs various operations and processes.

[0041] The processor 100 controls each part to realize various functions of the information processing device 30 based on programs such as firmware, system software, and application software stored in the ROM 101 or the RAM 102. The processor 100 executes processes based on the programs.

[0042] The processor 100, the ROM 101, and the RAM 102 are interconnected via the bus 103. The input / output interface 104 is also connected to this bus 103. The input unit 105, the output unit 106, the storage unit 107, the power supply 108, the imaging unit 15, and the analysis unit 20 are connected to the input / output interface 104.

[0043] The input unit 105 and the output unit 106 are user interfaces electrically connected to the input / output interface 104 by wire or wirelessly. The input unit 105 is composed of, for example, a keyboard, a mouse, etc., and inputs various information according to the user's instruction operation. The output unit 106 is composed of a display that displays the video imaged by the imaging unit 15, a speaker that amplifies sound, a printer, etc., and outputs images, sound, printed materials.

[0044] The storage unit 107 is an auxiliary storage device composed of an HDD (Hard Disk Drive), an SSD (Solid State Drive), etc. The storage unit 107 stores various types of information such as programs and setting values related to various processes. The storage unit 107 stores, for example, the component concentration of the above-mentioned honeycomb catalyst C and the component concentration of the coating layer, the denitration rate, and the determination reference value information described later as related information in which they are associated, and various programs and the like. When the honeycomb catalyst C is a three-way catalyst for an automobile, the storage unit 107 stores the determination reference value information described later as related information in which, for example, the component concentration of the catalyst components such as Pt, Rh, Pd, etc. and the component concentration of the coating layer are associated with the purification rate.

[0045] The functional configuration of the information processing apparatus 30 will be described with reference to FIG. 4. A control unit 110 described later that performs various controls of the information processing apparatus 30 is realized by a processor 100 described later that executes arithmetic processing executing programs stored in a ROM 101, a RAM 102, a storage unit 107, and the like.

[0046] The control unit 110 of the present embodiment includes an analysis result acquisition unit 111, a storage management unit 112, a quality determination unit 113, and an imaging processing unit 114. The analysis result acquisition unit 111 executes a process of acquiring analysis result information by the analysis unit 20.

[0047] The storage management unit 112 manages storage for various controls of the information processing apparatus 30. For example, for quality determination by the quality determination unit 113, the storage management unit 112 reads the determination reference value as related information in which the component concentration of the honeycomb catalyst C and the component concentration of the coating layer are associated with the denitration rate from the storage unit 107, and executes a process of storing it in the processor 100, the ROM 101, the RAM 102, and the like.

[0048] The determination reference value is related information associating the component concentration of the sample with the denitration rate. The denitration rate to be associated is the minimum value among the denitration rates that satisfy the required quality (hereinafter, may be referred to as the "minimum quality denitration rate"). The minimum quality denitration rate can be arbitrarily set. As a method for setting the determination reference value, for example, a method of previously analyzing a regeneration catalyst with a minimum quality denitration rate and deriving an absorbance based on the spectrum obtained by the analysis can be mentioned. The absorbance becomes the determination reference value as related information associated with the minimum quality denitration rate. The determination reference value is, for example, Al of the component of the coating layer 2 O 3 , SO 3 or the component concentration of TiO 2 of the honeycomb catalyst C is defined.

[0049] The memory management unit 112 executes a process of providing the above determination reference value to the quality determination unit 113 for quality determination by the quality determination unit 113. For example, the memory management unit 112 executes a process of providing the determination reference value to the quality determination unit 113 at the timing when the analysis result acquisition unit 111 acquires the analysis result from the analysis unit 20.

[0050] The quality determination unit 113 executes a process of determining the quality of the honeycomb catalyst C based on the component concentration derived from the analysis of the sample by the analysis unit 20. More specifically, the quality determination unit 113 executes a process of determining the quality of the honeycomb catalyst C based on the component concentration regarding the components of the honeycomb catalyst C and the components of the coating layer derived from the analysis by the analysis unit 20. The quality determination unit 113 according to the present embodiment is TiO as a component of the honeycomb catalyst C derived from the analysis by the analysis unit 20 2 , Al as a component of the coating layer 2 O 3 and SO 3 executes a process of determining the quality of the honeycomb catalyst C based on the component concentration.

[0051] The quality determination unit 113 compares the provided determination reference value with TiO obtained from the analysis result by the analysis unit 20 2 , Al 2 O 3 , and SO 3Compare with the component concentration. The quality determination unit 113 determines TiO obtained from the analysis result 2 When the component concentration of is equal to or higher than the determination reference value, or Al 2 O 3 And SO 3 When the component concentration of at least one of them is less than the determination reference value, it is determined that the quality is qualified. When the component concentration of TiO obtained from the analysis result 2 Is less than the determination reference value, or Al 2 O 3 And SO 3 When the component concentration of at least one of them is equal to or higher than the determination reference value, it is determined as unqualified.

[0052] In addition, when the honeycomb catalyst C is a three-way catalyst for an automobile, the quality determination unit 113 executes a process of determining the quality of the honeycomb catalyst C based on components such as Pt, Rh, Pd, etc. as components of the honeycomb catalyst C. In this case, when Pt, Rh, Pd, etc., which are catalyst components, are less than the determination reference value as related information, it is determined as unqualified on the grounds that the purification performance has deteriorated due to the coating layer formed on the catalyst. Further, when Pt, Rh, Pd, etc., which are catalyst components, are equal to or higher than the determination reference value as related information, the catalyst is determined as qualified on the grounds that the formed coating layer is thin and has the required purification performance.

[0053] The imaging processing unit 114 controls the imaging operation of the imaging unit 15. The quality determination device 1 according to the present embodiment is configured to control the imaging operation of the imaging unit 15 by the imaging processing unit 114 of the information processing device 30, but is not limited thereto, and may have a configuration for separately controlling the imaging unit 15.

[0054] Here, regarding the relationship between the component concentrations of TiO 3 , Al 2 O 3 And SO 3 And the denitration rate of the regenerated catalyst, an explanation will be given. Analysis was performed on the surfaces of five types of used catalysts with different denitration rates using an analyzer described later. Since it is estimated that samples of the same components are collected when samples are collected from the catalyst surface components, the surface components of the catalyst were analyzed.

[0055] The denitration rates of five types of used catalysts were measured by a known method in advance. The five types of used catalysts with different qualities were as follows: catalyst a before regeneration with a denitration rate of 37% at a molar ratio of 1.0, catalyst b after regeneration with a denitration rate of 76.6% at a molar ratio of 1.0, catalyst c with a denitration rate of 68.2%, catalyst d with a denitration rate of 68.9%, and catalyst e with a denitration rate of 74.4%.

[0056] The analysis using the analyzer was performed on three measurement points on the inner surface of the through hole C1 of the honeycomb catalyst C, the inlet portion M1, the middle portion M2, and the outlet portion M3 of the through hole C1 in the flow direction of the exhaust gas when the catalyst is in use.

[0057] In the analysis using the analyzer, the concentrations of the relevant components were obtained, and the relationship between the concentrations of the relevant components and the denitrification rate was confirmed. The relevant components are catalytic components, binder and ash components, and poisoning components. The catalytic components are components that make up the catalyst. The binder and ash components are components that originate from the catalyst and coal ash. The poisoning components are exhaust gas components that reduce catalytic activity. Specifically, the catalytic components are TiO 2 , WO 3 and V 2 O 5 The binder and ash components are SiO 2 , Al 2 O 3 , CaO and SO 3 The poisoning component is Na 2 OK 2 O and As 2 O 3 In the analysis, the concentration of each element is measured and converted to the relevant component to obtain the concentration of the relevant component. For example, if the relevant component is TiO 2 Or Al 2 O 3 , S.O. 3 If so, measure the component concentrations of Ti, Al, and S. The component concentrations of the individual elements obtained are converted into the component concentrations of the oxides.

[0058] As the analysis apparatus, measurement was performed using the "Scanning Fluorescent X-ray Analyzer ZSX Primus IV" manufactured by Rigaku Corporation. The measurement methods were qualitative analysis and simple quantification (quantitative calculation by the FP method (Fundamental Parameter method)). The measurement results are shown in Table 1. As described above, the component concentrations of the compounds in Table 1 are the values obtained by converting the component concentrations of the elemental substances into oxides.

[0059]

Table 1

[0060] Table 1 shows the ratios (mass %) of the catalyst components, binder-ash components, poisoning components, and other components for each of the catalysts a to e, for the inlet portion M1, intermediate portion M2, outlet portion M3 of the through-hole C1, and their average value AVE. The rightmost column of Table 1 shows the denitration rates for the catalysts a to e. When the component concentration could not be detected, etc., it is indicated by a hyphen.

[0061] For TiO of the catalyst component 2 it can be seen that, looking at the average of the measurement points M1 to M3, the component concentration increases as the denitration rate increases. For Al of the binder-ash component 2 O 3 and SO 3 it can be seen that, looking at the average of the measurement points M1 to M3, the component concentration decreases as the denitration rate increases. For Al of the binder-ash component 2 O 3 and SO 3 they are considered to be components of the coating layer.

[0062] Therefore, it can be said that there is a correlation between the denitration rate of the used catalyst and the component concentrations of TiO 2 , Al 2 O 3 and SO 3 Thus, the quality indicated by the denitration rate is related to TiO 2 , Al 2 O 3 and SO 3It can be said that it can be determined based on the component concentration. TiO 2 , Al 2 O 3 and SO 3 By previously deriving the related information in which the component concentrations of and the denitration rate are associated, the quality determination unit 113 can determine the quality of the honeycomb catalyst C based on the related information in which the component concentrations of TiO 2 , Al 2 O 3 and SO 3 derived by the analysis of the analysis unit 20 and the denitration rate are associated.

[0063] In other words, the quality determination unit 113 can determine the quality of the honeycomb catalyst C based on the determination reference value as the related information in which the component concentration of the sample and the denitration rate are associated.

[0064] For example, in the example of Table 1, when the denitration rate as the required performance for performance recovery is set to 74.0% or more, the determination reference value of TiO 2 as the related information can be defined as 81.0% for all of M1 to M3.

[0065] For example, in the example of Table 1, when the denitration rate as the required performance for performance recovery is set to 74.0% or more, the determination reference value of Al 2 O 3 as the related information can be defined as 1.5% for all of M1 to M3.

[0066] For example, in the example of Table 1, when the denitration rate as the required performance for performance recovery is set to 74.0% or more, the determination reference value of SO 3 as the related information can be defined as 2.5% for all of M1 to M3.

[0067] Therefore, when the quality determination unit 113 according to the present embodiment sets the passing standard for the quality of the catalyst to a denitration rate of 74.0% or more, the component concentration of TiO 2 derived by the analysis of the analysis unit 20 is 81.0% or more, and the component concentration of Al 2 O 3 is 1.5% or less, and SO3 When the component concentration of 3 satisfies at least one of them being 2.5% or less, the quality of the honeycomb catalyst C can be determined to be qualified.

[0068] Since the regeneration of the honeycomb catalyst C may not be uniform throughout the entire length of the through-holes, it is preferable to perform the quality determination at least at the inlet portion M1, the intermediate portion M2, and the outlet portion M3 of the through-hole C1.

[0069] As a specific determination method in this case, for example, the quality determination may be made based on the average value of the inlet portion M1, the intermediate portion M2, and the outlet portion M3. The quality determination may also be made based on the component concentration with the worst quality among the inlet portion M1, the intermediate portion M2, and the outlet portion M3.

[0070] In the above, the component concentration with the worst quality means, for example, when the component used for the determination is TiO 2 it indicates the component concentration with the lowest concentration, and when the component used for the determination is Al 2 O 3 or SO 3 it indicates the component concentration with the highest concentration.

[0071] The power supply 108 is configured to be able to supply power to each part of the information processing device 30 by being connected to an external power supply. The configuration capable of supplying power to the power supply is not limited to this, and for example, a battery may also be used.

[0072] <Quality Determination Method> Next, the quality determination method according to the present embodiment will be described with reference to FIG. 6. The quality determination method is the method using the above-described sample acquisition device 10. The quality determination method includes a separation step (step S10), a recovery step (step S11), an analysis step (step S12), and a quality determination step (step S13).

[0073] The quality determination method is not limited to the method for determining the quality of the catalyst after regeneration. For example, the quality determination method may determine the quality of the unused catalyst to confirm the performance of the catalyst, or may determine the quality of the catalyst during use to consider the timing of catalyst replacement. That is, the polishing in the polishing process is not limited to the polishing for determining the quality of the catalyst after regeneration. For example, the polishing in the polishing process may be performed to determine the quality of the unused catalyst to confirm the performance of the catalyst, or may be performed to determine the quality of the catalyst during use to consider the timing of catalyst replacement.

[0074] The separation step (step S10) is a step of separating a sample from the inner surface C1a of the through-hole C1 by the separation unit 11. The position for separating the sample is any one of the measurement points set in advance at several points in the longitudinal direction of the through-hole C1. It is preferable to collect at least the inlet portion M1, the intermediate portion M2, and the outlet portion M3 of the through-hole C1. This is because, as shown in Table 1 above, the component concentrations of the inner surface C1a are different at both ends and the central portion of the through-hole C1. However, the sampling location is not limited to this.

[0075] In the separation step (step S10), the separation unit 11 of the sample acquisition device 10 is inserted into the interior of any one of the plurality of through-holes C1, and the inner surface C1a of the through-hole C1 is scraped off by several μm to a dozen or so μm with the blade of the separation unit 11, and separated as a sample from the inner surface C1a of the through-hole C1.

[0076] When scraping, the imaging processing unit 114 may cause the imaging unit 15 to image the video near the sample and output it to the output unit 106 of the information processing device 30. While viewing the video near the sample imaged by the imaging unit 15, the inner surface C1a of the through-hole C1 can be scraped off, and the work can be performed efficiently.

[0077] The recovery process (step S11) is a process of recovering the sample separated in the separation process (step S10) by the recovery unit 14. Specifically, the opening on one end side of the sampling tube 12 is arranged near the sample separated in the separation process (step S10), and the suction operation inside the sampling tube 12 by the suction unit 13 is started. The sample separated from the inner surface C1a of the through hole C1 is sucked and circulated to the recovery unit 14 through the sampling tube 12 together with air, and is captured by the filter of the recovery unit 14. The suction operation by the suction unit 13 is stopped and the recovery process (step S11) is completed. In the recovery process (step S11), the sample in the recovery unit 14 may be moved to the analyzer 20b through the pipe 20a.

[0078] The analysis process (step S12) is a process of analyzing the components of the sample recovered in the recovery process (step S11). The components of the collected sample are measured by an analyzer 20b such as a fluorescent X-ray analyzer of the analysis unit 20. When sample pretreatment is required for the analysis by the analyzer 20b, the sample pretreatment may be performed.

[0079] The quality determination process (step S13) is a process of determining the quality of the honeycomb catalyst C based on the component concentrations analyzed in the analysis process (step S12). For example, the analysis result acquisition unit 111 of the information processing device 30 is made to acquire the analysis result analyzed by the analysis unit 20. Next, the storage management unit 112 of the information processing device 30 reads the determination reference values as related information in which the component concentrations of TiO 2 , Al 2 O 3 and SO 3 are associated with the denitration rate, and provides them to the quality determination unit 113. The quality determination unit 113 determines the quality of the honeycomb catalyst C based on the related information in which the component concentrations of TiO 2 , Al 2 O 3 and SO 3 derived from the analysis by the analysis unit 20 are associated with the denitration rate, and the quality determination process (step S13) is completed. Note that the catalyst targeted by this quality determination method is not limited to the denitration catalyst as described above, and is also applicable to catalysts used in blast furnaces of steelworks, three-way catalysts of automobiles, etc.

[0080] According to the sample acquisition device 10 according to the present embodiment described above, the following effects can be obtained. Since the performance of the denitration catalyst in a coal-fired power plant deteriorates when it continues to be used, it has been necessary to restore the performance such as replacing it with a new catalyst or regenerating the used catalyst. As a catalyst regeneration technology, mainly, a method of washing with water or chemicals, a method of impregnating the used catalyst with a catalyst active component again, and polishing are known as a method of physically scraping off the coating on the catalyst surface.

[0081] As quality control of the regeneration work, in the case of the method of washing or the method of impregnating the used catalyst with a catalyst active component, it is managed by performing reliable process control, visual inspection, extracting several catalysts as samples, and conducting inspections such as denitration rate, observation and component analysis of the catalyst surface, and component analysis of the catalyst itself. In the case of the method by polishing, in addition to the above-mentioned quality control, the wall thickness is measured at the timing before and after regeneration by polishing for all the catalysts to grasp and manage the polishing state.

[0082] The regenerated catalyst is obtained by regenerating the used catalyst, and since the usage conditions of individual catalysts are different, their states are not uniform. Therefore, even when regeneration is performed under the same conditions, unlike a new catalyst, there are many cases where the performance after regeneration does not become uniform.

[0083] Therefore, in order to ensure a certain level of quality, as a quality control method for the regenerated catalyst, simple inspections such as visual inspection and wall thickness measurement, and detailed inspections such as confirmation of the denitration rate, surface observation, and component analysis are performed. However, since the detailed inspection is a destructive inspection, it cannot be performed on all the regenerated catalysts. Therefore, the simple inspection is performed on all of them, and the detailed inspection is performed by sampling.

[0084] Furthermore, since the catalyst is as long as about several tens of cm to 1 m in the gas flow direction, polishing defects such as uneven polishing in the flow direction are likely to occur, and since the through holes are also long in the flow direction, for example, it may be difficult to perform a simple inspection and it may not be possible to detect the inside of the central part of the through hole or the like.

[0085] Furthermore, as described above, more precise quality control of the catalyst is assumed to be applicable not only to the quality control of the regenerated catalyst but also to catalysts that can be polished, such as unused catalysts and catalysts in use.

[0086] From the above, in order to improve the quality control accuracy of the catalyst, it was necessary to establish a simple inspection method that could be implemented for all products with the same accuracy as the detailed inspection. The sample acquisition device 10 according to the present invention can efficiently acquire a sample in the through-hole C1 of the honeycomb catalyst C for quality determination by high-precision measurement without destroying the honeycomb catalyst C.

[0087] As described above, some embodiments of the present invention have been described. However, these embodiments are merely examples and do not limit the technical scope of the present invention. The present invention can take various other embodiments, and furthermore, various changes such as omissions and substitutions can be made without departing from the gist of the present invention. These embodiments and their modifications are included in the scope and gist of the invention described in this specification and the like, and are also included in the invention described in the claims and its equivalent scope.

Explanation of Reference Numerals

[0088] C Honeycomb catalyst (catalyst) C1 Through-hole C1a Inner surface 10 Sample acquisition device 11 Separation unit 12 Sampling tube 13 Suction unit 14 Recovery unit

Claims

1. A sample acquisition device for acquiring a sample for quality determination from a through-hole of a catalyst, comprising: a separation unit capable of separating the sample from the inner surface of the through-hole; a sampling tube having the separation unit disposed at one end thereof and allowing the sample separated by the separation unit to flow therethrough; a suction unit capable of sucking the inside of the sampling tube from an opening at the other end of the sampling tube; a recovery unit for recovering the sample sucked through the sampling tube by the suction unit.

2. The sample acquisition device according to claim 1, further comprising an imaging unit provided at one end side of the sampling tube.

3. The separation unit has a blade, and the sample acquisition device according to claim 1 or 2, wherein the inner surface can be cut by the blade to separate the sample from the inner surface.

4. A quality determination device comprising: the sample acquisition device according to claim 1; an analysis unit for analyzing the sample recovered by the recovery unit; and a quality determination unit for determining the quality of the catalyst based on the component concentration derived from the analysis of the sample by the analysis unit.

5. The catalyst is a denitration catalyst, and the quality determination device according to claim 4, wherein the quality determination unit determines the quality of the catalyst based on the related information in which the component concentration of the sample and the denitration rate are associated.

6. The analysis unit measures, by analysis, at least the component concentration of at least one of Ti, Al, and S in the catalyst, and the quality determination device according to claim 5, wherein the quality determination unit determines the quality of the catalyst based on the related information in which the component concentrations of Ti, Al, and S measured by the analysis of the analysis unit and the denitration rate are associated. When the quality determination standard of the catalyst is set such that the denitration rate is 74.0% or more, the quality determination unit determines that the quality of the catalyst is qualified when the component concentration of TiO in terms of Ti measured by the analysis of the analysis unit is 81.0% or more, and the component concentration of Al in terms of Al is 1.5% or less, and the component concentration of SO in terms of S is 2.5% or less. The quality determination device according to claim 6. ２ converted component concentration is 81.0% or more, and Al of Al ２ O ３ converted component concentration is 1.5% or less, and SO of S ３ When the converted component concentration is 2.5% or less, the quality of the catalyst is determined to be qualified. The quality determination device according to claim 6.

7. The quality determination device according to claim 4 or 5, wherein the analysis unit is an X-ray analyzer.

9. A method for determining the quality of the catalyst using the sample acquisition device according to claim 1, comprising: a separation step of separating the sample from the inner surface by the separation unit; a recovery step of recovering the sample separated in the separation step by the recovery unit; an analysis step of analyzing the components of the sample recovered in the recovery step; and a quality determination step of determining the quality of the catalyst based on the component concentration analyzed in the analysis step.

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