JPH0989776A - Adsorption-species detection apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adsorption-species detection apparatus which is suitable for developing a practical catalyst for exhaust-gas purification and an absorbent for deodorization under an environment which is changed transiently. SOLUTION: An adsorption-species detection apparatus is provided with an infrared spectroscopic means 11 by which infrared rays from a sample S are detected and by which a substance existing on the surface of the sample is analyzed qualitatively and quantitatively and with a gas supply means by which component gases floping out from a plurality of gas containers 5A, 5B, 5C, 5D filled with different kinds of component gases are circulated to the sample S via a gas-supply-amount change means 6 which changes a gas supply amount. In addition, the adsorption-species detection apparatus is provided with a gas-composition control means 85 which controls the gas-supply-amount change means 6 in such a way that the composition of the gases circulating to the sample S is changed transiently, with a temperature change means 7 constituted of a resistance heating device 71 which heats the sample S steadily, of a laser heating device 72 which heats the sample in a large heating amount and of a cooling means 73 which cools circulating water and with a sample-temperature control means 86 which controls the temperature change means 7 in such a way that the temperature of the sample S is changed transiently.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adsorbed species detection device for analyzing a reaction mechanism of a catalyst and an adsorption mechanism of an adsorbent.

[0002]

2. Description of the Related Art An adsorbed species detecting device detects the reaction mechanism and desorption reaction by observing the behavior of unburned gas and odorous components on the surface of an exhaust gas purifying catalyst of an internal combustion engine and the adsorbent for deodorization. It is for the purpose of clarification, for example, the one using an infrared spectrometer is well known. This adsorbed species detection device detects infrared rays specific to a substance existing on the sample surface, and identifies or quantifies the substance present on the sample surface from an infrared spectrum obtained from the detected infrared rays.

[0003]

By the way, the evaluation of the catalyst and the adsorbent at the development stage using the above-mentioned adsorbed species detection device is carried out by passing a test gas, which is an exhaust gas component, through a sample in the catalyst. However, in an actual vehicle, the composition of the exhaust gas and the catalyst temperature change greatly depending on the running conditions, so a catalyst with excellent purification performance cannot be obtained in practical use unless the catalytic reaction accompanying these changes is evaluated. In addition, the adsorbent is adsorbed with various adsorption target substances, but the temperature changes greatly depending on the environment of use, so unless the reaction accompanying this change is evaluated, a practical deodorant can be obtained. I can't.
Further, when evaluating a catalyst or adsorbent having a non-simple shape, it is necessary to evaluate the influence of the shape on the action such as catalytic reaction.

Therefore, it is an object of the present invention to provide an adsorbed species detection device capable of transiently changing environmental conditions and suitable for developing practical catalysts and adsorbents. Further, according to the present invention, it is possible to observe a part of a microscopic area on the surface of a sample, evaluate the influence of the shape on the action such as a catalytic reaction, etc., and develop a catalyst and an adsorbent having a shape exhibiting practical performance. An adsorbed species detection device suitable for

[0005]

The apparatus for detecting an adsorbed species of the present invention detects a sample S from a sample S as shown in FIG. 1 in order to transiently change the composition of the gas flowing through the sample or the sample temperature during infrared spectroscopic measurement. Gas supply means for allowing a test gas to flow through the sample S in a variable composition in an adsorbed species detection device equipped with an infrared spectroscopic means 11 for detecting infrared rays and qualitatively or quantitatively detecting a substance existing on the surface of the sample S. 4A and a gas control means 85 for controlling the gas supply means 4A so that the composition of the test gas supplied by the gas supply means 4A changes transiently, and a sample temperature for heat exchange with the sample S in a variable sample temperature. At least one of the changing means 7 and the sample temperature control means 86 for controlling the sample temperature changing means 7 so that the temperature of the sample S changes transiently is provided (Claim 1).

The gas composition control means 85 is composed of a plurality of control elements which sequentially operate the gas supply means 4A in order to make the control easy to set environmental conditions. During the period of the element, each control element is set so that the target value of the composition of the test gas becomes constant (claim 2).

The gas supply means 4A is composed of a plurality of gases (4 in the figure) filled with different kinds of gases so as to transiently change the composition of the test gas supplied to the sample S with a simple structure. The container 5A, 5B, 5C, 5D and the gas supply amount changing means 6 for changing the gas supply amount supplied from each of the gas containers 5A to 5D to the sample S are provided (claim 3).

The sample temperature control means 86 is composed of a plurality of control elements which sequentially operate the control of the sample temperature changing means 7 in order in order to make the control easy to set environmental conditions. During the period of the control element, each control element is set so that the target value of the sample temperature changes constantly or linearly (claim 4).

The sample temperature changing means 7 has a simple structure and a steady heating means 71 for steadily heating the sample S so as to transiently change the temperature of the sample S, and the steady heating means 7.
1 comprises a transient heating means 72 for heating the sample S with a heating amount larger than the heating amount applied to the sample S, and a cooling means 73 for cooling the sample S (claim 5).

The transient heating means uses a laser heater 72 in order to efficiently apply a large amount of heat to only the sample S (claim 6).

The cooling means 73 has a water flow path 74 arranged around the sample S in order to efficiently remove heat from the sample S.
And a water supply means 75 for supplying water to the water flow path 74 (claim 7).

In another embodiment of the adsorbed species detection device of the present invention, infrared rays from a minute area on the surface of the sample S are collected by the adsorbed species detection device so that the site of the sample S can be evaluated. Microscopic means 12 for entering the infrared spectroscopic means 11
(Claim 8).

The adsorbed species detecting device of still another configuration of the present invention is infrared spectroscopic spectrum data detected by the infrared spectroscopic means 11 in each of the adsorbed species detecting devices so as to obtain the evaluation result of the adsorbed species substantially in real time. Is input, and an adsorbed species analysis means 8 for identifying an adsorbed species present on the surface of the sample S from the infrared spectrum data is provided (claim 9).

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION

(First Embodiment) An adsorbed species detection device of the present invention is shown in FIG. 1, and is an adsorbed species detection device that can be used for a catalyst, an adsorbent, or the like for general purposes. A Fourier infrared spectrometer (hereinafter referred to as “spectrometer”) 11 as an infrared spectroscopic means is arranged with its detection surface facing downward, and detects the intensity of infrared light incident on the detection surface. . The spectrometer 11 can be switched between a diffuse reflection type that detects diffuse reflection light from the sample and a radiation type that detects radiant light from the sample. Basically, the diffusion type is used when measuring the sample in the room temperature range and its vicinity, and the radiation type is used when measuring in the high temperature range of several hundred degrees or more. A mesh-shaped sample holding member 3 made of SUS is provided so as to face the detection surface of the spectrometer 11, and a pellet-shaped catalyst is held as the sample S. Sample holding member 3
Is mounted on a moving mechanism (not shown), and the position of the sample holding member 3 can be changed in the horizontal direction. Spectrometer 11
A microscope mechanism 12 as a microscopic means is disposed between the sample S and the sample S so that an observation site, which is a minute region on the surface of the sample S, is enlarged and projected on the detection surface of the spectrometer 11 via the microscope mechanism 12. It has become. The detection window 2 is provided between the sample S and the microscope mechanism 12, and partitions the sample S and the microscope mechanism 12. The detection window 2 has Zn at the opening of the partition wall 22A.
A flat plate 21 made of a material transparent to infrared light such as S is fitted, and infrared rays from the observation site on the surface of the sample S are flat plate 2
The light is incident on the microscope mechanism 12 via 1. A cooling water flow path 23 is formed in the detection window 2 along the outer edge of the flat plate 21 to prevent the temperature of the flat plate 21 from excessively rising due to a resistance heater 71 or the like which will be described later.
A computer 81 is provided with the output of the infrared spectrum detected by the spectrometer 11 as an input. Computer 8
1 and the spectrometer 11 bidirectionally communicate with each other, and while the spectrometer 11 transmits the infrared spectrum data to the computer 81, the computer starts and ends the measurement of the spectrometer 11. A signal for instructing is transmitted.

One of the sample holding members 3 communicates with each of the four mass flow controllers 62A, 62B, 62C and 62D connected in parallel via the test gas supply passage 41, and the other of the sample holding members 3 is connected. Communicates with the exhaust passage 42. Each of the mass flow controllers 62A to 62D is an on-off valve 61A, 61B, 6 constituting the gas supply amount changing means 6.
Gas cylinders 5A, 5 which are gas containers through 1C, 61D
B, 5C and 5D are connected by piping. The gas cylinders 5A to 5D are filled with CO, NO, O2, and C3 H6, which are the component gases of the model gas as the test gas. A model gas control device 85 for instructing the opening degree is connected to each of the mass flow controllers 62A to 62D, and a D / A converter provided with an opening degree instruction signal at an output portion of the model gas control device 85. The D / A conversion is performed by, and the operation of each mass flow controller 62A to 62D is controlled. Further, the model gas control device 85 transmits an opening / closing instruction signal to the opening / closing valves 61A to 61D,
The kind of the component gas of the model gas can be arbitrarily combined. Mass flow controller 62A-62D
The on-off valves 61A to 61D form the gas supply amount changing means 6, and the composition of the gas, that is, CO, NO, O2, C3 H6.
The ratio and flow rate are set. The opening degree instruction signal to the mass flow controllers 62A to 62D and the opening / closing signal to the opening / closing valves 61A to 61D are output according to the gas supply sequence programmed in the model gas control device 85. Also, the mass flow controller 62A
62D to 62D, the data of the flow rate control results in the mass flow controllers 62A to 62D is the model gas control device 85.
The A / D converter provided in the input section of the A / D converter A / D converts the data into the model gas control device 85. The model gas control device 85 and the computer 81 communicate with each other bidirectionally, and while the computer 81 transmits the data of the gas supply sequence to the model gas control device 85, the model gas control device 85 transmits the data to the computer 8 as well.
1, the data of the flow rate control results of the mass flow controllers 62A to 62D is transmitted.

A water channel 74 is provided so as to pass through the outside of the sample holding member 3, and the water flowing through the water channel 74 and the sample S
Heat is exchanged between and via the sample holding member 3. A water pump 75, which is a water supply means, is connected to the water flow path 74 by a pipe, and the water flow path 74 and the water pump are connected to each other.
A circulating water flow path is formed with the pump 75 to form a cooling means 73. A resistance heater 71 is arranged further on the outer periphery of the water channel 74, and heats the sample S via the water channel 74 and the sample holding member 3. A laser heater 72 is arranged so as to face the bottom surface of the sample holding member 3, and the sample S is irradiated with laser light through the sample holding means 3. The resistance heater 71, the laser heater 72, and the cooling unit 73 constitute the sample temperature changing unit 7.

A temperature detector 9 is provided above the sample holding member 3 toward the sample S so as to detect the radiation temperature of the sample S.

The water pump 75, the resistance heater 71, and the laser heater 72 are connected to a temperature controller 86, which is a sample temperature control means, so that power is supplied to each of them. The temperature detection signal output from the temperature detector 9 is input to the temperature controller 86. Temperature controller 8
6 monitors the temperature detection signal in accordance with a temperature change sequence which will be described later programmed therein, and feedback-controls the power supply to the water pump 75, the resistance heater 71, and the laser heater 72. It has become. The temperature controller 86 and the computer 81 communicate with each other bidirectionally, and the computer 81 sends the temperature change sequence data to the temperature controller 86 while the temperature controller 86 sends the temperature detector 9 to the computer 81. The temperature data detected by is transmitted.

A keyboard 82 is provided on the computer 81.
Is connected, and the user can set and input the data of the gas supply sequence and the data of the sample temperature change sequence. Also, the computer 81
A CRT 83 is connected to the device to display the experimental results and the like. An information storage medium (for example, a hard disk or MO disk) 84A is connected to the computer 81 so that the infrared spectroscopy spectrum data obtained in the evaluation test, the sample temperature aging data, and the like can be stored. There is. The information storage medium 84A has a computer 8
1, a program for identifying the adsorbed species to be executed on 1), an adsorbed species relating to the catalyst, a database of the catalytic reaction, etc. are stored. The program is the infrared spectrum data output from the spectrometer, the data of the model gas flowing through the sample S output from the model gas control device 85, the sample temperature, and the adsorption related to the catalyst stored in the information storage medium 84A. The adsorbed species are identified by referring to the data of the species and the catalytic reaction database. The adsorbed species detecting means 8A includes a computer 81, an information storage medium 84A, a keyboard 82 and the like.
Is doing.

The operation of the adsorbed species detection device will be described. FIG. 2 shows a flow of software for creating measurement sequence data of the adsorbed species detection device, which comprises a gas supply sequence part, a sample temperature change sequence part, and an infrared spectroscopy sequence part. The creation software is read from the information storage medium 84A and executed on the computer 81. The user inputs a setting from the keyboard 82 according to the display on the CRT 83 in an interactive mode with the computer 81.

The sample temperature changing sequence is composed of a plurality of consecutive control elements which characterize the change in the target temperature of the sample S from the start to the end of the evaluation test, and each sequence step is steadily and linearly. A simple temperature profile of any one of three types, that is, a steady temperature increase that changes the temperature, a transient temperature increase that transiently changes the temperature linearly, and a temperature hold that holds the final temperature of the immediately preceding sequence step is formed. An arbitrary temperature history is simulated by combining sequence steps having different contents. In the sample temperature change sequence part of the above-mentioned creation software, the temperature profile of each sequence step is set and input. First, the number N of sequence steps of the sample temperature change sequence is input (step 10
0). The sequence step number N represents the number of sequence steps from the start to the end of the evaluation test, and N from sequence step 0 to sequence step N-1.
Sequence steps are set. Set the temperature profile of each sequence step by the following procedure. First, it is input whether the temperature is maintained or the steady temperature rise or the transient temperature rise is performed (step 120). If the temperature rise is selected (step 130), then it is input whether the temperature rise is transient or steady (step 140). When the steady temperature increase is selected (step 150), the target temperature (hereinafter, reached temperature) in the sequence step is input (step 151), and then the time to reach the reached temperature (hereinafter, reached time) (step 152) Enter. When holding is input in step 120, step 130
To 170, the time for holding the final temperature of the immediately preceding sequence step (hereinafter, holding time) is input. If you selected transient changes in step 140,
The process proceeds from step 150 to step 161, the reached temperature is input in the same manner as when the steady temperature increase is selected (step 161), and then the arrival time is input (step 16).
2). In this way, each sequence step i (i = 0
~ N-1) setting is completed (step 110)
Then, the process proceeds to step 200 to set the gas supply sequence data.

The gas supply sequence consists of consecutive control element sequence steps which characterize the change in the target value of the composition of the model gas flowing through the sample S from the start to the end of the evaluation test. Each sequence step
During that period, the model gas composition is constant. By combining sequence steps in which the composition of the model gas is different, an arbitrary change with time of the composition of the model gas flowing through the sample S is simulated. In the gas supply sequence part of the creation software, the composition of the model gas in each sequence step is set and input. First, the number of steps G of the gas supply sequence is input (step 200). The number of steps G indicates the number of sequence steps from the start to the end of the evaluation test, and G sequence steps from sequence step 0 to sequence step G-1 are set. The composition ratio of the model gas in each sequence step is set by the following procedure. Types of gas filled in the gas cylinders 5A to 5D (CO, N
The composition ratio is input for each of O, O2, and C3 H6 (step 220), and then the time period of the sequence step is set (step 230). When the setting is completed for each sequence step j (j = 0 to G-1) (step 210), the process proceeds to step 240 to set the infrared spectroscopy sequence data.

In setting the infrared spectrum sequence data, the measurement start time for starting the measurement is input to the spectrometer 11 (step 240), then the measurement is ended in the spectrometer 11 and the infrared spectrum output by the spectrometer 11 is output. The time when the data is taken into the computer is input (step 250).

The data of the sample temperature change sequence, the gas supply sequence, and the infrared spectroscopy sequence are stored in the information storage medium 8.
4A (step 260) and the setting of each sequence is completed. 4 (A), FIG. 4 (B), and FIG.
4 (C), FIG. 4 (D), and FIG. 4 (E) show an example of the temperature change sequence data and the gas supply sequence data set by the creation software, and FIG.
In (A), the sample S temperature is steadily raised from room temperature to 600 degrees Celsius in the first sequence step, the sample S temperature is kept constant in the subsequent sequence step, and then 6 degrees Celsius.
The sequence step of transiently raising the temperature from 00 degrees to 800 degrees Celsius is repeated multiple times. Then, after a sequence step in which the temperature of the sample S is kept constant, the temperature is returned to room temperature again.

FIGS. 4B to 4 showing the composition of the model gas
In (E), the first sequence step continues until the sample temperature S transiently rises, and then the sequence step at 0.5 minute intervals continues for several times, during which CO, NO, C3
H6 changes in a pulsed manner with a constant cycle. O2 is CO
While the changes such as show a pulse-like behavior, the initial value (2
2%, which is less than 0%, will remain constant. in this way,
Complex environmental conditions can be simulated by combining simple temperature profile sequence steps and model gas composition constant sequence steps.

When measuring, the spectrometer 11 is switched to either a diffuse reflection type or a radiation type according to the sample S temperature drawn from the setting data of the sample temperature changing sequence. After holding the sample S to be measured on the sample holding member 3, the position of the sample holding member 3 is adjusted so that the observation site of the sample S is projected onto the detection surface of the spectrometer 11 via the microscope mechanism 12. .

The operation of the adsorbed species detection device during measurement will be described. FIG. 3 shows a computer 81 when performing an evaluation test.
First, the data of the set measurement sequence is read from the information storage medium 84A (step 3).
00), the read data is transmitted to the temperature controller 86 and the model gas control device 85. The temperature controller 86 and the model gas controller 85 are programmed by the transmitted data (steps 311, 312). Then, the temperature controller 86 and the model gas control device 85 are instructed to start the sequence (step 320), and a timer for counting the time from the start to the end of the evaluation test is started (step 330).

The gas supply sequence and the sample temperature changing sequence proceed independently from sequence step 0. The model gas control device 85 sends an opening / closing signal to each of the on-off valves 61A to 61D according to the programmed gas supply sequence to open only the on-off valve communicating with the gas cylinder filled with the gas that is a component of the model gas. Then, the opening instruction signal is transmitted to each of the mass flow controllers 62A to 62D, and the mass flow controllers 62A to 62D are sent.
Is each gas cylinder 5A to 5D at a flow rate according to the opening instruction signal
The component gas of the model gas flows out from the. The component gases that have flowed out are mixed in the test gas supply path 41 and flow into the surface of the sample S. On the other hand, the mass flow controllers 62A to 62
The data of the flow rate control amount of D is input to the computer 81 via the model gas control device 85. The data input to the computer 81 is temporarily held by the computer 81 and then stored in the information storage medium 84A.

The temperature controller 86 operates the resistance heater 71, the laser heater 72, and the water pump 73 in accordance with the programmed temperature change sequence to heat or cool the sample S according to the set temperature profile.
In the sequence step in which the steady temperature rise is set, the resistance heater 71 heats the sample S temperature at the set ultimate temperature and ultimate velocity. In the sequence step set to transient heating,
The laser heater 72 irradiates the sample S with laser through the mesh-shaped sample holding member 3, and the sample S becomes the resistance heater 71.
By the above, the temperature is raised from the state of constant heating at the reached temperature and the set arrival time. The cooling water is circulated in the water flow path 74 by the water pump 75, and the sample S is cooled by exchanging heat with the sample S via the sample holding member 3.

On the other hand, during the evaluation test, the temperature detection data from the temperature detector 9 is input to the computer 81 via the temperature controller 86 at a time interval which can be said to be substantially real time, and is temporarily held by the computer 81. After that, it is stored in the information storage medium 84A.

Until the measurement start time comes, step 35
The routine proceeds from 0 to step 370 and returns to step 340 again to repeat the data such as the gas composition and the sample S temperature from the temperature controller 86 and the model gas controller 85.

The measurement start time comes (step 350)
And instruct the spectrometer 11 to start measurement (step 36).
0). Infrared rays are emitted from the surface of the sample S, and this infrared ray has a spectrum peculiar to the substance existing on the surface of the sample S. The spectrometer 11 detects infrared light from the surface of the sample S which is incident on the detection surface of the spectrometer 11 via the microscope mechanism 12. Infrared light is detected a plurality of times, and infrared spectroscopic spectrum data with high detection value accuracy is obtained. At the data acquisition time (step 370), the spectrometer 11
The above data is fetched from (step 380). The computer 81 is a database of the adsorbed species and the catalytic reaction stored in the information storage medium 84A based on the data of the infrared spectrum taken in, the data of the composition of the model gas and the like.
The types of chemical components contained in the adsorbed species are identified and quantified from the gas. The infrared spectrum and the result of identification of the adsorbed species are stored in the information storage medium 84A.

Until all the sequence steps are completed, the process returns from step 390 to step 340,
Data acquisition from the temperature controller 86 and the model gas control device 85 (step 340), measurement by the spectrometer 11,
The data acquisition from the spectrometer 11 (step 380) is repeated. During the evaluation test, the type of adsorbed species and the like as well as the temporal data such as the temperature of the sample S and the composition of the test gas are output to the CRT 83 as a test report. When all the steps are completed (step 390), the evaluation test is completed.

In the above-mentioned adsorbed species detection device, the infrared spectroscopic measurement can be performed by reproducing the change in the environmental condition simulated by the measurement sequence data creation software in the device.
Further, it is possible to selectively observe a minute area of the sample.

(Second Embodiment) FIG. 5 shows another embodiment of the present invention, which is an adsorbed species detecting device used for evaluation of an exhaust gas purifying catalyst. In the figure, the parts denoted by the same reference numerals as those in FIG. 1 are substantially the same, and therefore differences will be mainly described.

The gas supply means 4B is a gasoline engine 4
3 and a fuel tank 44 for supplying fuel to the gasoline engine 43. An unillustrated exhaust port of the gasoline engine 43 communicates with the sample holding member 3.
An engine control circuit 87, which is a gas supply control unit, is connected to the gasoline engine 43.
It opens and closes the throttle and controls the air-fuel ratio. Engine control circuit 87 and computer 81
And a gasoline engine 43 from the computer 81 to the engine control circuit 87.
While transmitting the control sequence data, the engine control circuit 45 transmits to the computer 81 the data of the throttle opening / closing of the controlled gasoline engine 43 and the air fuel ratio.

A reflection plate 76 is provided obliquely above the sample holding member 3, and the laser heater 72 once reflects the light on the reflection plate 76 to irradiate the surface of the sample S with laser light. ing. An information storage medium 84B is connected to the computer 81, and instead of the measurement sequence data creation software, another measurement sequence data creation software including the sample temperature change sequence part and the engine control circuit 87 sequence part. I remember. In the sequence portion of the engine control circuit 87 of the measurement sequence data creation software, the throttle opening degree and the air fuel ratio in each sequence step are set to simulate the operation of the gasoline engine 43.

The operation of the adsorbed species detection device will be described below.
First, the measurement sequence data set in advance and stored in the information storage medium 84B is loaded from the information storage medium 84B to the engine control circuit 87 and the temperature controller 86, and the measurement is started. When the engine control circuit 45 operates the gasoline engine 43 according to the simulation, the exhaust gas discharged from the gasoline engine 43 causes the test gas supply passage 41 to be exhausted.
Flow through to the surface of the sample S. The composition and flow rate of the exhaust gas in each sequence step correspond to the simulated throttle opening and air-fuel ratio, and transient changes such as during actual engine acceleration proceed. On the other hand, as in the first embodiment, the laser heater 72 and the like operate according to the programmed temperature changing sequence, and the temperature of the sample S changes.

The exhaust gas flowing on the surface of the sample S causes the catalytic reaction to proceed on the surface of the sample S. Adsorbed species such as intermediate products in the reaction process are excited by heat from the laser heater 72 and the like to emit infrared rays specific to each substance. This infrared ray is detected by the spectrometer 11, and the data of the detected infrared spectrum is transmitted to the computer 81.

The above-mentioned adsorbed species detection apparatus can reproducibly cause an actual transient change of the engine and observe the behavior of the sample surface under transient heating. In the adsorbed species detection device, if the air-fuel ratio of the gasoline engine 43 is set within an appropriate range, particulates can be generated in the exhaust gas. By changing the temperature of the sample S transiently by the laser heater 72, the behavior of the particulate in the state where the temperature changes transiently can be observed.

(Third Embodiment) FIG. 6 shows still another embodiment of the present invention, which is an adsorbed species detecting apparatus mainly used for evaluating an adsorbent. In the figure, the parts denoted by the same reference numerals as those in FIG. 1 are substantially the same, and therefore differences will be mainly described.

The above-mentioned adsorbed species detection device is configured to omit the gas supply means 4A, the model gas control device 85, the circulating water flow path 23 for cooling the flat plate 21 of the detection window 2 and the like of the adsorbed species detection device of FIG. Information storage medium 84C of host device 8C
In place of the measurement sequence data creation software shown in FIG. 2, the measurement sequence data creation software consisting only of the sample temperature change sequence part and the infrared spectroscopy sequence part is stored in the memory. Further, in the information storage medium 84C, instead of the database related to the catalyst, the adsorption species related to the adsorbent and the reaction database are stored.
The adsorbed species detection device has a simple structure so that only a transient change in temperature is observed. An adsorbent sample S such as activated carbon, silica, or alumina is attached to the sample holding member 3
Place it in a predetermined test atmosphere before holding it in
Then, the sample S is held by the sample holding member 3. In the evaluation test, the laser heater 72 or the like is operated, and the sample S temperature is changed according to the programmed sample temperature change sequence under the test atmosphere in which the gas composition is constant. The state of the functional group of the adsorbed species and the desorption reaction of the adsorbed species on the surface of the sample S can be observed.

In each of the above-mentioned embodiments, the temperature change is transiently generated. However, the resistance heater 71, the laser heater 72, the water pump 75 and the like are omitted from the adsorption species detection device of FIG. Only the composition of may be changed transiently.

In the first embodiment, the component of the test gas is C
Although O, NO, O2 and C3 H6 are used, other gases may be used. When evaluating the adsorbent, NH3 or the like is used as the adsorption target substance of the adsorbent. The number of types of gas may be more or less than four.

The microscope mechanism need not be used for observing a powder sample or observing a minute area of the sample. Atmosphere data such as sample temperature and infrared spectral data are stored in an information storage medium without adsorbed species analysis means, and adsorbed species are identified by a separate adsorbed species analysis means after measurement is completed. May be.

The infrared spectroscopic means can be appropriately selected from infrared spectrometers, Fourier transform infrared spectrometers, Raman spectrometers, Fourier transform Raman spectrometers, etc. other than those described in the above embodiments. . Although the method of switching between the diffuse reflection type and the radiation type was adopted, if the sample temperature range to be evaluated is only one of the normal temperature range and its vicinity, or the high temperature range,
The spectrometer need only be equipped with either one. The sample holding member may be heated by a high frequency heater or an infrared heater instead of the resistance heater. A resistance temperature detector or a thermocouple may be provided in contact with the sample instead of the temperature detector that detects the radiation temperature. The material of the sample holding member is SUS, but any material other than a catalytic metal substance that interacts with the sample, such as alumina or platinum, may be used. The material of the flat plate forming the detection window is ZnS, but ZnSe or the like may be used as long as it has transparency to infrared rays and heat resistance according to the reproduced heat state. Although the gasoline engine is used in the second embodiment,
It may be an internal combustion engine such as a diesel engine, a methanol engine, an LPG engine, etc., and exhaust gas discharged from them may be circulated on the surface of the sample to evaluate the catalyst.

[0047]

As described above, according to the adsorbed species detection device of the present invention, the environmental conditions can be changed transiently, and it is suitable for the development of practical catalysts and adsorbents. In addition, it is possible to observe a small area on the sample surface, and to evaluate the influence of the shape on the action such as catalytic reaction.
It is suitable for the development of catalysts and adsorbents with shapes that demonstrate practical performance.

[Brief description of drawings]

FIG. 1 is an overall view of an adsorbed species detection device of the present invention.

FIG. 2 is a flowchart for explaining the operation of the adsorbed species detection device of the present invention.

FIG. 3 is another flowchart explaining the operation of the adsorbed species detection device of the present invention.

4 (A), (B), (C), (D) and (E) are first, second, third, fourth and fifth explaining the operation of the adsorbed species detection device of the present invention. Is a time chart of.

FIG. 5 is an overall view of another adsorbed species detection device of the present invention.

FIG. 6 is an overall view of still another adsorbed species detection device of the present invention.

[Explanation of symbols]

 11 infrared spectrometer (infrared spectroscopic means) 12 microscope mechanism (microscopic means) 4A, 4B gas supply means 5A, 5B, 5C, 5D gas cylinder (gas container) 6 gas supply amount changing means 7 sample temperature changing means 71 resistance heating Vessel (steady-state heating means) 72 laser heater (transient heating means) 73 cooling means 74 water flow path 75 water pump (water supply means) 8A, 8B, 8C adsorbed species analysis means 85 model gas controller (sample temperature) Control means) 86 Temperature controller (gas composition control means) 87 Engine control circuit (gas composition control means)

Claims (9)

[Claims] 1. An adsorbed species detection apparatus equipped with infrared spectroscopic means for detecting infrared rays from a sample and qualitatively and quantitatively detecting a substance present on the surface of the sample, wherein a composition of a test gas is variable in the sample. A gas supply means to be circulated and a gas composition control means for controlling the gas supply means so that the composition of the test gas supplied by the gas supply means changes transiently, and a sample for exchanging heat with the sample in a variable sample temperature. An adsorbed species detection device comprising at least one of a temperature changing means and a sample temperature control means for controlling the sample temperature changing means so that the sample temperature changes transiently. 2. The adsorbed species detection device according to claim 1, wherein the gas composition control means is composed of a plurality of control elements for sequentially controlling the gas supply means in time series.
An adsorbed species detection device in which each control element is set so that the target value of the composition of the test gas is constant during the period of each control element. 3. The adsorbed species detection device according to claim 1, wherein the gas supply means is provided with a plurality of gas containers filled with different kinds of gas, and a gas supply amount supplied from each gas container to the sample. An adsorbed species detection device comprising a gas supply amount changing means for changing the above. 4. The adsorbed species detection device according to claim 1, wherein the sample temperature control means is composed of a plurality of control elements for sequentially operating the control of the sample temperature changing means in time series. An adsorbed species detection device in which the above-mentioned control elements are set so that the target value of the sample temperature changes constantly or linearly during the control element period. 5. The adsorbed species detecting device according to claim 1, wherein the temperature changing means is larger than a steady heating means for constantly heating the sample and a heating amount applied to the sample by the steady heating means. An adsorbed species detection device comprising a transient heating means for heating the sample with a heating amount and a cooling means for cooling the sample. 6. The adsorbed species detection device according to claim 5, wherein a laser heater is used as the transient heating means. 7. The adsorbed species detection device according to claim 5 or 6, wherein the cooling means is composed of a water flow path arranged around the sample and water supply means for supplying water to the water flow path. Species detector. 8. The adsorbed species detection device according to claim 1, further comprising a microscopic unit that collects infrared rays from a minute area on the surface of the sample and makes them incident on the infrared spectroscopic unit. . 9. The adsorbed species detection device according to claim 1, wherein the infrared spectroscopic spectrum data detected by the infrared spectroscopic means is input, and the adsorbed species present on the sample surface is identified from the infrared spectroscopic spectrum data. An adsorbed species detection device equipped with adsorbed species analysis means.