All-quartz in-situ infrared transmission device

Abstract

The utility model provides an all-quartz in-situ infrared transmission device. The device comprises a sample cell, a sample holder, a joint and a variable-temperature passage, the top of the sample cell is provided with an interface, two sides of the sample cell in the first horizontal direction are respectively provided with a window, and a light path is formed between the two windows; a sample area is arranged at the lower end of the sample rack; the sample holder is provided with a temperature measurement passage and a gas passage; the lower end of the temperature measuring channel extends to the sample area and is used for arranging a temperature measuring element; the temperature measuring element can measure the temperature of the position of the sample; the gas passage is used for introducing atmosphere gas or a probe into the sample area or performing variable pressure treatment; the connector is arranged in the middle of the sample holder, the sample holder is arranged at the interface of the sample pool through the connector, so that the lower part of the sample holder is positioned in the sample pool, and the sample area is positioned in the light path; the variable-temperature passage part is arranged corresponding to the sample area; the variable-temperature passage is used for introducing a first variable-temperature medium, and the first variable-temperature medium can change the temperature of the sample area.

Description

Technical Field

[0001] This disclosure relates to an all-quartz in-situ infrared transmission device. Background Technology

[0002] In the petrochemical industry, 80% of refining processes and chemical material synthesis processes involve the application of catalytic materials and catalytic reaction processes. The structure of the active centers of catalytic materials and changes in reaction processes are closely related to their performance. Currently, the acquisition and research focus of this information remains on molecular spectroscopy, especially infrared spectroscopy. After catalytic materials undergo a series of treatments such as reduction, sulfidation, oxidation, and purification to bring them as close as possible to their reaction state, in-situ adsorption of appropriate probe molecules can be performed. Changes in infrared characteristic peaks can reveal structural information such as the type, intensity, distribution, and accessibility of surface acid-base centers and metal active centers. In-situ characterization of reactant model molecules, by collecting infrared characteristic peaks on the catalyst surface, can reveal the adsorption-desorption properties of the reactants, capturing information about adsorbed species, intermediates, and products. Through the acquisition of this rich information, further in-depth analysis of the surface reaction mechanism, combined with evaluation data on catalytic activity and reaction selectivity, provides crucial information and support for catalyst preparation optimization and precise process control.

[0003] In-situ infrared spectroscopy measurements require integrated in-situ devices that meet specific requirements. However, existing sample cells for in-situ infrared spectroscopy measurements often fail to meet the in-situ processing needs of cutting-edge research. For example, existing high-temperature gas-solid reaction cells, whether made entirely of metal or containing metal components, are unsuitable for corrosive environments and strongly acidic substances, as well as for cryogenic measurements. While some reports suggest that in-situ cells can handle corrosive atmospheres, this requires separating processing and measurement into two separate parts and sample transfer, resulting in large volumes and preventing simultaneous in-situ measurements under corrosive gas conditions. In the field of in-situ infrared detection, common variable-temperature reaction cells struggle to achieve low-temperature and ultra-low-temperature detection conditions. However, under certain research conditions, lowering the temperature is necessary to elicit vibrational signals from specific gas molecules. Therefore, developing in-situ infrared characterization techniques for cryogenic applications is essential. In-situ spectroscopic characterization of sulfide catalysts, which are widely used in the field of petroleum catalysis, requires the sample to be cooled to liquid nitrogen temperature for probe adsorption. However, the current in-situ metal cell part uses gas-carried liquid nitrogen for cooling, and the measured limit temperature is only -160℃. Moreover, the cooling time is long and the amount of liquid nitrogen consumed is large, which cannot reach -190℃, thus affecting accurate and complete characterization. Utility Model Content

[0004] A primary objective of this disclosure is to overcome at least one of the deficiencies of the prior art and to provide a corrosion-resistant, adsorption-resistant, and easy-to-clean all-quartz in-situ infrared transmission device.

[0005] To achieve the above objectives, the present disclosure adopts the following technical solution:

[0006] According to one aspect of this disclosure, an all-quartz in-situ infrared transmission device is provided, comprising: a sample cell, a sample holder, a connector, and a temperature-changing passage; the sample cell, sample holder, connector, and temperature-changing passage are all made of quartz; the top of the sample cell is provided with an interface, and windows are respectively provided on both sides of the sample cell in a first horizontal direction, forming a light path extending along the first horizontal direction between the two windows for infrared light emitted from external optical equipment to pass through and for signal collection from the sample; the lower end of the sample holder has a sample area for accommodating the sample; the sample holder is provided with a temperature measurement passage and a gas passage, both of which are quartz sleeves. The temperature measurement path extends from the upper end of the sample holder to the sample area. The temperature measurement path is used to house a temperature measuring element capable of measuring the temperature at the sample location. The gas path is used to introduce atmospheric gas, a probe, or a pressure transformer into the sample area. The connector is located in the middle of the sample holder, and the sample holder is connected to the sample pool interface via the connector, so that the lower part of the sample holder is located within the sample pool, and the sample area is located within the light path. The variable temperature path is partially arranged corresponding to the sample area. The variable temperature path is used to introduce a first variable temperature medium, which can change the temperature of the sample area.

[0007] According to one embodiment of this disclosure, the temperature-changing passage includes a first temperature-changing passage that is introduced from the upper end of the sample holder and extends to the sample area.

[0008] According to one embodiment of this disclosure, the temperature-changing passage includes two first temperature-changing passages, which are arranged at intervals along the first horizontal direction, and the lower ends of the two first temperature-changing passages are respectively located on both sides of the sample area in the first horizontal direction.

[0009] According to one embodiment of this disclosure, the temperature-changing passage includes a second temperature-changing passage disposed in the sample pool and arranged around the lower end of the sample holder.

[0010] According to one embodiment of this disclosure, the connector is provided with a ground joint structure and is disposed at the interface of the sample pool via the ground joint structure.

[0011] According to one embodiment of this disclosure, the all-quartz in-situ infrared transmission device further includes a first temperature-changing medium tank, which is made of quartz profile; the first temperature-changing medium tank is disposed on the outer periphery of the joint and is used to introduce a second temperature-changing medium, which can prevent the joint from being too cold or too hot.

[0012] According to one embodiment of this disclosure, each of the two windows is provided with an infrared window pane.

[0013] According to one embodiment of this disclosure, the sample cell includes a main body and two medium tank receiving portions. The interface is connected to the top of the main body, and the two medium tank receiving portions are respectively connected to both sides of the main body in the first horizontal direction. The window is opened on the side of the medium tank receiving portion facing away from the main body. The all-quartz in-situ infrared transmission device further includes two second variable-temperature medium tanks, which are made of quartz profiles. The two second variable-temperature medium tanks are respectively housed in the two medium tank receiving portions and are used to introduce a third variable-temperature medium, which can prevent the infrared window from being too cold or too hot.

[0014] According to one embodiment of this disclosure, the all-quartz in-situ infrared transmission device further includes a first temperature-changing medium tank, which is made of a quartz profile; the first temperature-changing medium tank is disposed on the outer periphery of the joint and is used to introduce a third temperature-changing medium, the third temperature-changing medium can prevent the joint from being too cold or too hot; wherein, the first temperature-changing medium tank and the second temperature-changing medium tank are connected through a temperature-changing medium passage so that the third temperature-changing medium can circulate in the first temperature-changing medium tank and the second temperature-changing medium tank.

[0015] According to one embodiment of this disclosure, the gas passage includes an inlet passage and an outlet passage; the inlet passage is connected to the sample area to serve as an introduction channel for atmospheric gas or a probe or a pressure transformation channel; the outlet passage is connected to the connector to serve as an outlet channel for atmospheric gas or a probe or a pressure transformation channel; wherein, the gas passage includes at least two inlet passages, and the at least two inlet passages are respectively connected to the sample area.

[0016] As can be seen from the above technical solution, the advantages and positive effects of the all-quartz in-situ infrared transmission device proposed in this disclosure are as follows:

[0017] The all-quartz in-situ infrared transmission device disclosed herein includes a sample cell, a sample holder, a connector, and a temperature-changing passage. An interface is provided at the top of the sample cell, and windows are respectively provided on both sides of the sample cell in a first horizontal direction, forming a light path between the two windows. A sample area is located at the lower end of the sample holder. The sample holder is provided with a temperature measurement passage and a gas passage. The lower end of the temperature measurement passage extends to the sample area and is used to arrange a temperature measuring element, which can measure the temperature at the location of the sample. The gas passage is used to introduce atmospheric gas, a probe, or a pressure-changing process into the sample area. The connector is located in the middle of the sample holder, and the sample holder is connected to the interface of the sample cell via the connector, so that the lower part of the sample holder is located within the sample cell, and the sample area is located within the light path. The temperature-changing passage is arranged corresponding to the sample area. The temperature-changing passage is used to introduce a first temperature-changing medium, which can change the temperature of the sample area. Through the above structural design, this disclosure realizes an in-situ infrared transmission device made entirely of quartz material, which can meet the cutting-edge scientific research needs such as corrosive gas treatment and sulfide and strong acid catalytic materials. The overall structure of the device is compact and reasonable, suitable for meeting the design requirements of small volume, and easy to operate. At the same time, this disclosure can simultaneously meet high temperature treatment and ultra-low temperature detection by utilizing a variable temperature path, avoiding device deformation or cracking caused by large temperature difference changes. It has good airtightness, long service life, low cost, and good market prospects. Attached Figure Description

[0018] The various objectives, features, and advantages of this disclosure will become more apparent from the following detailed description of preferred embodiments of the disclosure taken in conjunction with the accompanying drawings. The drawings are merely illustrative illustrations of the disclosure and are not necessarily drawn to scale. In the drawings, the same reference numerals always denote the same or similar parts. Wherein:

[0019] Figure 1 This is a schematic diagram of the structure of an all-quartz in-situ infrared transmission device according to an exemplary embodiment;

[0020] Figure 2 yes Figure 1 The diagram shows the structure of the sample cell;

[0021] Figure 3 yes Figure 1 The diagram shows the structure of the sample holder;

[0022] Figure 4 This is the infrared spectrum of the adsorption probe molecule C at -190℃ after the oxidized catalyst A is subjected to high-temperature in-situ sulfidation.

[0023] Figure 5 This is the infrared spectrum of probe molecule C adsorbed at -190℃ after high-temperature in-situ oxidation of superacid catalyst B.

[0024] Figure 6The infrared spectrum of the adsorption probe molecule C at -160℃ after the oxidized catalyst A is subjected to high-temperature in-situ sulfidation.

[0025] Figure 7 This is the infrared spectrum of probe molecule C adsorbed at -190℃ after high-temperature in-situ oxidation of superacid catalyst B.

[0026] The annotations in the attached figures are explained as follows:

[0027] 100. Sample cell;

[0028] 101. Main body;

[0029] 102. Medium tank receiving section;

[0030] 110. Interface;

[0031] 120. Window;

[0032] 121. Infrared window;

[0033] 130. Second variable temperature pathway;

[0034] 140. Second variable temperature medium bath;

[0035] 200. Sample rack;

[0036] 210. Sample area;

[0037] 220. Temperature measurement pathway;

[0038] 231. Air intake passage;

[0039] 232. Vent passage;

[0040] 240. First temperature-controlled passage;

[0041] 300. Connector;

[0042] 310. First variable temperature medium bath;

[0043] 311. Variable temperature medium passage;

[0044] P. Light path;

[0045] T. Temperature measuring element;

[0046] X. First horizontal direction. Detailed Implementation

[0047] Typical embodiments embodying the features and advantages of this disclosure will be described in detail in the following description. It should be understood that this disclosure can have various variations in different embodiments without departing from the scope of this disclosure, and the descriptions and drawings therein are illustrative in nature and not intended to limit this disclosure.

[0048] In the following description of various exemplary embodiments of this disclosure, reference is made to the accompanying drawings, which form part of this disclosure, and which illustrate by way of example different exemplary structures, systems, and steps that can implement various aspects of this disclosure. It should be understood that other specific embodiments of the components, structures, exemplary devices, systems, and steps may be used, and structural and functional modifications may be made without departing from the scope of this disclosure. Furthermore, while the terms “above,” “between,” “within,” etc., may be used in this specification to describe different exemplary features and elements of this disclosure, these terms are used herein only for convenience, such as the orientation according to the examples described in the accompanying drawings. Nothing in this specification should be construed as requiring a specific three-dimensional orientation of the structure to fall within the scope of this disclosure.

[0049] See Figure 1 The illustration shows a schematic diagram of the all-quartz in-situ infrared transmission device proposed in this disclosure. In this exemplary embodiment, the all-quartz in-situ infrared transmission device is described using an in-situ reaction apparatus applied to in-situ infrared characterization as an example. It will be readily understood by those skilled in the art that various modifications, additions, substitutions, deletions, or other changes may be made to the specific embodiments described below to apply the relevant designs of this disclosure to other types of reaction apparatuses; these changes remain within the scope of the principles of the all-quartz in-situ infrared transmission device proposed in this disclosure.

[0050] like Figure 1 As shown, in one embodiment of this disclosure, the all-quartz in-situ infrared transmission device includes a sample cell 100, a sample holder 200, a connector 300, and a temperature-changing passage. (See also...) Figure 2 and Figure 3 , Figure 2 The diagram shows a representative structural schematic of the sample cell 100 that embodies the principles of this disclosure; Figure 3 The accompanying drawing represents a schematic diagram of the sample holder 200, which embodies the principles of this disclosure. Specifically, the drawing shows cross-sectional views of the internal structures of components such as the sample cell 100 and the sample holder 200. The structure, connection methods, and functional relationships of the main components of the all-quartz in-situ infrared transmission device proposed in this disclosure will be described in detail below with reference to the accompanying drawings.

[0051] like Figures 1 to 3As shown, in one embodiment of this disclosure, the design employs an all-quartz material, meaning the sample cell 100, sample holder 200, connector 300, and temperature-changing passage are all made of quartz. Specifically, the sample cell 100 has an interface 110 at its top, and windows 120 are respectively provided on both sides of the sample cell 100 in the first horizontal direction X. A light path P extending along the first horizontal direction X is formed between these two windows 120, allowing infrared light emitted from external optical equipment (e.g., an infrared spectrometer) to pass through and for sample signal collection. The light path P is parallel to the infrared light path, and the specific structure of the quartz profile can be optimized according to the size of the sample (e.g., a sample sheet) and the sample chamber size of the infrared spectrometer. The windows 120 at both ends of the light path P are the same size as the windows of the infrared spectrometer. The lower end of the sample holder 200 has a sample area 210 for accommodating the sample. The sample holder 200 has a fixing function, accommodating and fixing the sample sheet perpendicular to the light path P. The shape and thickness of the sample holder 200 can be optimized according to the size of the sample sheet, maximizing the area of ​​the sample sheet exposed in the light path P. The sample holder 200 is equipped with a temperature measurement path 220 and a gas path, both of which are quartz tubes. The upper end of the temperature measurement path 220 extends from the upper end of the sample holder 200, and the lower end extends to the sample area 210. The temperature measurement path 220 is used to house a temperature measuring element T (e.g., a cylindrical thermocouple or resistance temperature detector), which measures the temperature at the sample location. The specific structure of the quartz tube in the temperature measurement path 220 can be optimized according to the size of the thermocouple or resistance temperature detector required for the measured temperature range. The lower end of the temperature measurement path 220 can be directly connected to the sample holder 200 and in direct contact with the sample. The gas path is used to introduce atmospheric gas, probes, or pressure transformers into the sample area 210. The connector 300 is located in the middle of the sample holder 200. The sample holder 200 is connected to the interface 110 of the sample cell 100 via the connector 300, so that the lower part of the sample holder 200 is located within the sample cell 100, and the sample area 210 is located in the light path P. The temperature-changing path is a quartz sleeve, part of which is arranged corresponding to the sample area 210. The temperature-changing path is used to introduce a first temperature-changing medium, which can change the temperature of the sample area 210. Depending on the temperature requirements, the first temperature-changing medium can be one or more media. Specifically, a heating medium can be selected as the first temperature-changing medium according to the heating range and rate requirements, a cooling medium can be selected as the first temperature-changing medium according to the cooling range and rate requirements, or a combination of heating and cooling media can be selected as the first temperature-changing medium according to the cooling range and rate requirements.Through the above structural design, this disclosure realizes an in-situ infrared transmission device made entirely of quartz material, which can meet the cutting-edge scientific research needs such as corrosive gas treatment and sulfide-state and strong acid catalytic materials. The overall structure of the device is compact and reasonable, suitable for meeting the design requirements of small volume, and easy to operate. At the same time, this disclosure can simultaneously meet high-temperature treatment and ultra-low temperature detection by utilizing a variable temperature path, avoiding device deformation or cracking caused by large temperature difference changes. It has good airtightness, long service life, low cost, and good market prospects. In addition, the upper and lower parts of this disclosure (i.e., sample holder 200 and sample cell 100) can be quickly opened and closed through a connector 300. After the two parts are combined, in-situ characterization, ventilation or vacuuming, high and low temperature variable temperature treatment, and real-time acquisition of infrared spectra can be performed. When the two parts are separated, all-round cleaning without dead angles can be performed.

[0052] like Figure 1 and Figure 3 As shown, in one embodiment of this disclosure, the temperature-changing pathway may include a first temperature-changing pathway 240, which is introduced from the upper end of the sample holder 200 and extends to the sample region 210. Through the above structural design, this disclosure can utilize the first temperature-changing pathway 240 to achieve temperature regulation of the sample region 210.

[0053] like Figure 1 and Figure 3 As shown, based on the structural design of the temperature-changing path including the first temperature-changing path 240, in one embodiment of this disclosure, the temperature-changing path may include two first temperature-changing paths 240. These two first temperature-changing paths 240 are arranged at intervals along the first horizontal direction X, and the lower ends of the two first temperature-changing paths 240 are respectively located on both sides of the sample region 210 in the first horizontal direction X. Through the above structural design, this disclosure can utilize the two first temperature-changing paths 240 extending to both sides of the sample region 210 to make the temperature adjustment of the sample region 210 more uniform, and can improve the temperature change rate and increase efficiency. In some embodiments, the sample holder 200 may also be provided with only one, three or more first temperature-changing paths 240, and is not limited to this embodiment.

[0054] Based on the structural design of the temperature-changing passage including the first temperature-changing passage 240, in one embodiment of this disclosure, the lower end of the first temperature-changing passage 240 can be U-shaped, and both ends of the first temperature-changing passage 240 are led out from the upper end of the sample holder 200. In some embodiments, the first temperature-changing passage 240 may also adopt other shapes according to actual needs, and is not limited to this embodiment.

[0055] like Figure 1 and Figure 2As shown, in one embodiment of this disclosure, the temperature-changing path may include a second temperature-changing path 130, which is disposed in the sample pool 100. When the sample holder 200 is assembled with the sample pool 100 such that the lower end of the sample holder 200 is located within the sample pool 100, the second temperature-changing path 130 is arranged around the lower end of the sample holder 200. Through the above structural design, this disclosure can utilize the second temperature-changing path 130 to achieve temperature regulation of the sample area 210. Furthermore, by organically combining the first temperature-changing path 240 and the second temperature-changing path 130, this disclosure can achieve a more effective temperature-changing function. It should be noted that the structure shown in the accompanying drawings is only schematic; the second temperature-changing path 130 is actually arranged to avoid the light path P, and the two do not interfere with each other in space, thereby ensuring the smooth passage of infrared light.

[0056] It should be noted that, Figures 1 to 3 The illustrated embodiment uses an all-quartz in-situ infrared transmission device comprising two variable-temperature paths (i.e., a first variable-temperature path 240 and a second variable-temperature path 130) as an example. It should be understood that in various possible embodiments conforming to the design concept of this disclosure, the number of variable-temperature paths may also be one, that is, only one of the aforementioned first variable-temperature path 240 and second variable-temperature path 130 may be provided, and this embodiment is not limited thereto.

[0057] Based on the structural design of the temperature-changing pathway, which includes a first temperature-changing pathway 240 and a second temperature-changing pathway 130, in one embodiment of this disclosure, during the heating process, the first temperature-changing pathway 240 can wrap around the sample one or more times, or a heating element or heating block can be built into the temperature-changing pathway to further improve the temperature controllability. During the cooling process, a cooling medium can be added to at least one of the first temperature-changing pathway 240 and the second temperature-changing pathway 130, such as liquid nitrogen (up to -194°C) or liquid helium (up to -200°C).

[0058] In one embodiment of this disclosure, the connector 300 may be provided with a ground joint structure, and the connector 300 may be disposed at the interface 110 of the sample cell 100 via this ground joint structure. Specifically, the connector 300 may be wedge-shaped with an outer ground joint structure on its outer periphery, or the connector 300 may be sleeve-shaped with an inner ground joint structure on its inner periphery. In other words, the connector 300 and the interface 110 may be connected in an upper and lower wedge shape or in parallel. Through the above structural design, this disclosure can utilize the ground joint structure to enhance the friction between the connector 300 and the interface 110, improve the connection strength between the sample holder 200 and the sample cell 100 via the connector 300, and ensure good sealing between the two.

[0059] like Figure 1 and Figure 3As shown, in one embodiment of this disclosure, the all-quartz in-situ infrared transmission device may further include a first temperature-changing medium tank 310, which is constructed of a quartz profile. Specifically, the first temperature-changing medium tank 310 is disposed on the outer periphery of the connector 300, and is used to introduce a second temperature-changing medium (e.g., water or other solvent), which prevents the connector 300 from becoming too cold or too hot. Through the above structural design, this disclosure can prevent the connector 300 from being damaged due to overheating or overcooling by appropriately introducing the second temperature-changing medium into the first temperature-changing medium tank 310 for circulation, while also preventing the condensation of water vapor in the environment.

[0060] like Figure 1 and Figure 2 As shown, in one embodiment of this disclosure, the two windows 120 of the sample cell 100 can each be provided with an infrared window 121. The material of the infrared window 121 can be selected according to actual needs, such as, but not limited to, calcium fluoride. Through the above structural design, this disclosure can utilize the infrared window 121 to close the window 120 and maintain the sealed environment of the sample cell 100 after vacuuming for a long time (preferably the vacuum environment can reach 1×10). -4 This further optimizes the stability of the sample measurement environment and improves the accuracy of the measurement. Meanwhile, the infrared window 121 used in this disclosure does not affect the passage of infrared light. In some embodiments, the window 120 of the sample cell 100 may not have an infrared window 121; that is, the window 120 can be directly open, and this is not limited to this embodiment.

[0061] Based on the structural design of the window 120 of the sample cell 100 having an infrared window 121, in one embodiment of this disclosure, the infrared window 121 can be made of one of calcium fluoride, zinc selenide, or potassium chloride.

[0062] like Figure 1 and Figure 2As shown, based on the structural design of the sample cell 100 with an infrared window 121 provided in the window 120, in one embodiment of this disclosure, the sample cell 100 may include a main body 101 and two medium tank receiving portions 102. Specifically, the interface 110 of the sample cell 100 is connected to the top of the main body 101, and the two medium tank receiving portions 102 are respectively connected to both sides of the main body 101 in the first horizontal direction X. The window 120 of the sample cell 100 is opened on the side of the medium tank receiving portion 102 facing away from the main body 101. Based on this, the all-quartz in-situ infrared transmission device proposed in this disclosure may also include two second variable-temperature medium tanks 140, which are made of quartz profiles. The two second variable-temperature medium tanks 140 are respectively housed in the two medium tank receiving portions 102, and the second variable-temperature medium tanks 140 are used to introduce a third variable-temperature medium (e.g., water or other solvent), which can prevent the infrared window 121 from being overcooled or overheated. Through the above structural design, this disclosure can prevent the infrared window 121 from being damaged due to overheating or overcooling by appropriately introducing a third temperature-changing medium into the second temperature-changing medium tank 140 for circulation, thereby ensuring a closed environment in the sample cell 100 and preventing the condensation of water vapor in the environment.

[0063] like Figure 1 As shown, in one embodiment of this disclosure, the all-quartz in-situ infrared transmission device may simultaneously include the aforementioned first variable-temperature medium tank 310 and second variable-temperature medium tank 140. Based on this, the first variable-temperature medium tank 310 and the second variable-temperature medium tank 140 may be connected via a variable-temperature medium passage 311, which may be a quartz tube. Specifically, the variable-temperature medium passage 311 may include four parts: one connected to an external gas source and the first variable-temperature medium tank 310; another connected to the first variable-temperature medium tank 310 and one of the second variable-temperature medium tanks 140; a third connected to both second variable-temperature medium tanks 140; and a fourth connected to the other second variable-temperature medium tank 140 and the external gas source. Accordingly, when the first variable-temperature medium tank 310 and the second variable-temperature medium tank 140 are connected, the aforementioned second and third variable-temperature media may be the same medium, allowing the variable-temperature media to circulate within the first and second variable-temperature medium tanks 310 and 140.

[0064] like Figure 1 and Figure 2As shown, in one embodiment of this disclosure, the gas passage may include an inlet passage 231 and an outlet passage 232. Specifically, the inlet passage 231 is connected to the sample area 210 of the sample holder 200, and can serve as an introduction channel for atmospheric gas or probes, or a pressure-changing processing channel. The outlet passage 232 is connected to the connector 300, and can serve as an outlet channel for atmospheric gas or probes, or a pressure-changing processing channel. Accordingly, when atmospheric gas is introduced, gas enters through the inlet passage 231 and exits through the outlet passage 232; during vacuuming, at least one of the inlet passage 231 and the outlet passage 232 is connected to a vacuum system; when a probe molecule is introduced, it can be introduced through the inlet passage 231 or vacuumed through the outlet passage 232; when multiple probe molecules are introduced, they can be introduced through the inlet passage 231 and the outlet passage 232, respectively or simultaneously. Based on this, the gas passage may include at least two gas inlet passages 231, which are respectively connected to the sample region 210. Through the above structural design, this disclosure can introduce at least two different atmospheric gases or probes using at least two gas inlet passages 231 according to the experimental design, thereby expanding the application scope of this disclosure and meeting more complex experimental needs.

[0065] It should be noted that the all-quartz in-situ infrared transmission apparatus shown in the accompanying drawings and described in this specification are merely a few examples among many apparatuses capable of employing the principles of this disclosure. It should be clearly understood that the principles of this disclosure are by no means limited to any detail or component of the all-quartz in-situ infrared transmission apparatus shown in the accompanying drawings or described in this specification.

[0066] Based on the detailed description of several exemplary embodiments of the all-quartz in-situ infrared transmission device proposed in this disclosure above, a specific embodiment, two usage examples, and two comparative examples of this disclosure will be described below.

[0067] Example:

[0068] In a specific embodiment of this disclosure, the aforementioned optical device can be an infrared spectrometer, specifically a Fourier transform infrared spectrometer. The infrared window is a circular calcium fluoride window, and the sample holder is a 14mm diameter, top-opening quartz tube with only one connector, which is a wedge-shaped quartz sleeve with an external ground joint. One of the first variable-temperature channels has a heating wire inserted around the sample sheet, and a temperature measurement channel has a resistance temperature detector (RTD). The temperature control device is a voltage output and electronic temperature feedback control system with a temperature control accuracy of 1°C. The other first and second variable-temperature channels are circulated with liquid nitrogen during cooling; this can be circulated or controlled by the temperature feedback control system. The first and second variable-temperature medium tanks are connected via variable-temperature medium channels and connected to a circulating water device, whose flow rate and temperature are controlled by the circulating water device. The gas channel is equipped with a control valve and a flow control device, a vacuum system and a vacuum testing device, and a probe molecule controllable gas inlet device. Based on the above design, direct measurement of high-temperature heating can reach up to 600℃, and direct measurement of liquid nitrogen cooling can reach -194℃, with rapid heating or cooling to the required temperature within 20 minutes. The preferred vacuum pumping capacity is 1×10⁻⁶. -4 Pa.

[0069] Example 1: In-situ characterization of low-temperature probe adsorption after high-temperature sulfidation and high-temperature purification of oxidized catalyst.

[0070] Oxidized catalyst A is a white solid powder. A small amount is pressed into a 14mm diameter circular ultrathin sample sheet and placed on the sample holder to fix it in place without shaking. The upper and lower joints of the device are joined together, ensuring the ground joints fit snugly, and a vacuum is applied. This device is fixed in the sample chamber of the infrared spectrometer, so that the sample sheet is precisely positioned in the optical path and the signal is at its maximum. Circulating water is introduced into the variable temperature medium passage and controlled by a circulation device.

[0071] A mixture of hydrogen and hydrogen sulfide (5%) is introduced through the inlet passage at a flow rate controlled at 30 ml / min, and exits through the outlet passage. The catalyst is heated to 400°C using a first variable-temperature heating device, sulfided for 2 hours, and then cooled. A vacuum is then created through the inlet passage, and the temperature is raised to 200°C using another first variable-temperature heating device, purified for 1 hour, and then cooled. Liquid nitrogen is then injected through a second and a third variable-temperature heating device to lower the temperature to -194°C in approximately 20 minutes. Probe molecules C are then introduced through the inlet passage to perform in-situ infrared desorption spectroscopy at different temperatures. This allows for the determination of the distribution of active sites after in-situ sulfidation of the catalyst and the electron-deficient states as a function of temperature.

[0072] Figure 4 The infrared spectrum of the oxidized catalyst A after high-temperature in-situ sulfidation and adsorption of probe molecule C at -190℃ is shown. The characteristic peaks a and b of the support on A and the characteristic peaks c and d of the active metal phases of different sulfidation states of the catalyst are visible. The characteristic peaks are clear and obvious, and are easy to separate and quantify.

[0073] Example 2: In-situ characterization of high-temperature oxidation and low-temperature probe adsorption of superacid catalysts.

[0074] Superacid catalyst B is a white solid powder. A small amount was pressed into a 14mm diameter circular ultrathin sample sheet and placed on the sample holder of the all-quartz in-situ characterization device, fixed in place to prevent movement. The upper and lower joints of the device were assembled, ensuring a tight fit between the ground joints. A vacuum test was conducted, achieving a yield of 1×10⁻⁶. -4 The device has good airtightness (Pa). It is fixed in the sample chamber of the infrared spectrometer, ensuring the sample is positioned precisely in the optical path and the signal is at its maximum. Circulating water is introduced into the variable-temperature medium passage, controlled by a circulation device.

[0075] Air is introduced through the inlet passage at a controlled flow rate of 40 ml / min and flows out through the outlet passage. The temperature is raised to 450℃ using a first variable-temperature heating device, cooled after 2 hours, and then evacuated through the inlet passage. The temperature is then raised to 200℃ using another first variable-temperature heating device, purified for 1 hour, and then cooled. Liquid nitrogen is then injected through a second and a third variable-temperature passage for further cooling, reaching -194℃ in approximately 20 minutes. Probe molecules C are then introduced through the inlet passage for in-situ infrared desorption spectroscopy at different temperatures. This allows for the determination of the acidic center distribution after in-situ catalyst oxidation and the intensity of the acidic centers as a function of temperature.

[0076] Figure 5 The infrared spectrum of probe molecule C adsorbed at -190℃ after high-temperature in-situ oxidation of superacid catalyst B is shown. The characteristic peaks e, f, g and h corresponding to the acidic center on B are clearly visible.

[0077] Comparative Example 1: In-situ characterization of low-temperature probe adsorption after high-temperature sulfidation and high-temperature purification of oxidized catalyst.

[0078] This embodiment uses one of the best-performing commercially available in-situ metal baths. The sample preparation and in-situ adsorption steps are similar to those in Example 1 above. The specific implementation plan is as follows:

[0079] Catalyst A, an oxidized white solid powder, was placed in a small amount on a metal sample holder. The device was then capped, and its airtightness was tested under vacuum. The airtightness was found to be as low as 1 × 10⁻⁶. -2 Pa. The in-situ device was fixed in the sample chamber of the infrared spectrometer, ensuring the sample was precisely positioned in the optical path and the signal was at its maximum. A mixture of hydrogen and hydrogen sulfide (5%) was introduced at a flow rate of 30 ml / min. The temperature was programmed to rise to 400 °C, and after 2 hours of sulfidation, the temperature was lowered, and a minimum vacuum of 1 × 10⁻⁶ was applied. -2Pa, the temperature is programmed to 200℃, purified for 1 hour, and then cooled. Then, it is cooled by gaseous and liquid nitrogen, down to a minimum of -160℃. Probe molecules C are introduced, and infrared in-situ desorption spectroscopy is performed to obtain the distribution of active centers after in-situ sulfidation of the catalyst.

[0080] Figure 6 The infrared spectrum of the oxidized catalyst A after high-temperature in-situ sulfidation is shown at -160℃, and is compared with that of the above-mentioned usage example. Figure 4 In comparison, it is evident that the characteristic peaks a and b corresponding to the support on A have undergone significant changes, and the ratio of characteristic peaks c and d of different sulfide-state metal active phases of the catalyst has also changed, failing to achieve the desired effect. Figure 3 The in-situ characterization effect of the present invention is not as good as that of the present invention in terms of low temperature performance and vacuum sealing. Therefore, the characterization of the active center is not complete and accurate.

[0081] Compared with the sample holder and sample chamber after in-situ sulfidation reaction, the sample holder of this disclosure is white and clean, while the sample holder of Comparative Example 1, which was originally the metal in-situ cell after characterization, has been sulfided and turned black, which is irreversible and difficult to clean. The residual hydrogen sulfide will have a significant impact on the in-situ reaction of other catalysts, such as Comparative Example 2.

[0082] Comparative Example 2: In-situ characterization of high-temperature oxidation and low-temperature probe adsorption of superacid catalysts.

[0083] This embodiment uses one of the best-performing commercially available in-situ metal baths. The sample preparation and in-situ adsorption steps are similar to those in Example 2 above. The specific implementation plan is as follows:

[0084] Superacid catalyst B is a white solid powder. A small amount was placed on a metal sample holder, the device cap was closed, and the airtightness was tested by vacuum testing. The airtightness was as low as 1×10⁻⁶. -2 Pa. The in-situ device was fixed in the sample chamber of the infrared spectrometer, ensuring the sample was precisely positioned in the optical path and the signal was at its maximum. Air was introduced at a flow rate of 40 ml / min, the temperature was programmed to 450 °C, oxidation was carried out for 2 hours, followed by cooling, and a minimum vacuum of 1 × 10⁻⁶ was applied. -2 Pa, the temperature is raised to 200℃, purified for 1 hour, and then cooled. Then, it is cooled by gaseous and liquid nitrogen to a minimum of -160℃. Probe molecules C are introduced to perform in-situ infrared desorption and spectroscopy to observe the distribution of acidic centers after in-situ oxidation of the catalyst.

[0085] Figure 7 The infrared spectrum of probe molecule C adsorbed at -160℃ after high-temperature in-situ oxidation of superacid catalyst B is compared with that of Example 2 above. Figure 5 In comparison, it is evident that the characteristic peaks e, f, g, and h corresponding to the acidic center on B have all undergone significant changes. (Failed to achieve...) Figure 4The in-situ characterization effect of the present invention is not as good as that of the present invention in terms of low temperature performance and vacuum sealing. Therefore, the characterization of the active center is not complete and accurate.

[0086] Compared with the state of the sample after the in-situ oxidation reaction, the sample in the embodiment of this disclosure is still white and the color has changed after the reaction. After the in-situ characterization of the comparative example, the sample contains a lot of black powder. Since the material of the in-situ cell has been sulfided and turned black, the residual hydrogen sulfide will partially react with the catalyst at high temperature, which will have a significant impact on its in-situ characterization, and the results are no longer accurate.

[0087] In summary, the all-quartz in-situ infrared transmission device proposed in this disclosure includes a sample cell 100, a sample holder 200, a connector 300, and a temperature-changing passage. The sample cell 100 has an interface 110 at its top, and windows 120 are respectively provided on both sides of the sample cell 100 in the first horizontal direction X, forming a light path P between the two windows 120. The sample holder 200 has a sample area 210 at its lower end. The sample holder 200 is provided with a temperature measurement passage 220 and a gas passage. The lower end of the temperature measurement passage 220 extends to the sample area 210 and is used to arrange temperature measuring elements. The temperature measuring element T measures the temperature at the location of the sample. The gas passage is used to introduce atmospheric gas, a probe, or a pressure transformer into the sample area 210. The connector 300 is located in the middle of the sample holder 200, and the sample holder 200 is connected to the interface 110 of the sample cell 100 via the connector 300, so that the lower part of the sample holder 200 is located inside the sample cell 100, and the sample area 210 is located in the light path P. The variable temperature passage is arranged corresponding to the sample area 210. The variable temperature passage is used to introduce a first variable temperature medium, which can change the temperature of the sample area 210. Through the above structural design, this disclosure realizes an in-situ infrared transmission device made entirely of quartz material, which can meet the cutting-edge scientific research needs such as corrosive gas treatment and sulfide and strong acid catalytic materials. The overall structure of the device is compact and reasonable, suitable for meeting the design requirements of small volume, and easy to operate. At the same time, this disclosure can simultaneously meet high temperature treatment and ultra-low temperature detection by utilizing a variable temperature path, avoiding device deformation or cracking caused by large temperature difference changes. It has good airtightness, long service life, low cost, and good market prospects.

[0088] The exemplary embodiments of the all-quartz in-situ infrared transmission device proposed in this disclosure have been described and / or illustrated in detail above. However, the embodiments of this disclosure are not limited to the specific embodiments described herein; rather, components and / or steps of each embodiment may be used independently and separately from other components and / or steps described herein. Each component and / or step of one embodiment may also be used in combination with other components and / or steps of other embodiments. In describing the elements / components / etc. described and / or illustrated herein, the terms "a," "an," and "the above" are used to indicate the presence of one or more elements / components / etc. The terms "comprising," "including," and "having" are used to indicate an open-ended inclusion and to mean that additional elements / components / etc. may exist in addition to the listed elements / components / etc. Furthermore, the terms "first" and "second," etc., in the claims and description are used only as illustrative marks and are not intended to limit the numerical scope of the object.

[0089] Although the all-quartz in-situ infrared transmission apparatus of this disclosure has been described according to different specific embodiments, those skilled in the art will recognize that modifications may be made to the implementation of this disclosure within the spirit and scope of the claims.

Claims

1. A fully quartz in-situ infrared transmission device, characterized in that: It includes a sample cell (100), a sample holder (200), a connector (300), and a variable temperature passage; The sample cell (100), sample holder (200), connector (300), and temperature-changing passage are all made of quartz. The sample cell (100) is provided with an interface (110) at the top. The sample cell (100) is provided with windows (120) on both sides in the first horizontal direction (X). The sample cell (100) forms a light path (P) extending along the first horizontal direction (X) between the two windows (120) to allow infrared light emitted by external optical devices to pass through and to collect the sample signal. The sample holder (200) has a sample area (210) at its lower end for accommodating samples; the sample holder (200) is provided with a temperature measurement passage (220) and a gas passage, both of which are quartz sleeves; the upper end of the temperature measurement passage (220) extends from the upper end of the sample holder (200), and its lower end extends to the sample area (210); the temperature measurement passage (220) is used to arrange a temperature measuring element (T), which can measure the temperature at the location of the sample; the gas passage is used to introduce atmospheric gas, a probe, or a pressure transformer into the sample area (210). The connector (300) is disposed in the middle of the sample holder (200), and the sample holder (200) is disposed at the interface (110) of the sample pool (100) via the connector (300) so that the lower part of the sample holder (200) is located in the sample pool (100), and the sample area (210) is located in the light path (P); The temperature-changing passage is a quartz sleeve, which is partially arranged corresponding to the sample area (210); the temperature-changing passage is used to introduce a first temperature-changing medium, which can change the temperature of the sample area (210).

2. The all-quartz in-situ infrared transmission device according to claim 1, characterized in that, The temperature-changing pathway includes a first temperature-changing pathway (240), which is introduced from the upper end of the sample holder (200) and extends to the sample area (210).

3. The all-quartz in-situ infrared transmission device according to claim 2, characterized in that, The temperature-changing pathway includes two first temperature-changing pathways (240), which are arranged at intervals along the first horizontal direction (X), and the lower ends of the two first temperature-changing pathways (240) are respectively located on both sides of the sample area (210) in the first horizontal direction (X).

4. The all-quartz in-situ infrared transmission device according to claim 1, characterized in that, The temperature-changing passage includes a second temperature-changing passage (130), which is disposed in the sample pool (100) and arranged around the lower end of the sample holder (200).

5. The all-quartz in-situ infrared transmission device according to claim 1, characterized in that, The connector (300) is provided with a ground joint structure and is disposed at the interface (110) of the sample cell (100) via the ground joint structure.

6. The all-quartz in-situ infrared transmission device according to claim 1, characterized in that, The all-quartz in-situ infrared transmission device also includes a first temperature-changing medium tank (310), which is made of quartz profile; the first temperature-changing medium tank (310) is disposed on the outer periphery of the joint (300) and is used to introduce a second temperature-changing medium, which can prevent the joint (300) from being too cold or too hot.

7. The all-quartz in-situ infrared transmission device according to claim 1, characterized in that, The two windows (120) are each provided with an infrared window (121).

8. The all-quartz in-situ infrared transmission device according to claim 7, characterized in that, The sample cell (100) includes a main body (101) and two medium tank receiving parts (102). The interface (110) is connected to the top of the main body (101). The two medium tank receiving parts (102) are respectively connected to the two sides of the main body (101) in the first horizontal direction (X). The window (120) is opened on the side of the medium tank receiving part (102) facing away from the main body (101). The all-quartz in-situ infrared transmission device also includes two second variable temperature medium tanks (140), which are made of quartz profiles. The two second variable temperature medium tanks (140) are respectively housed in the two medium tank receiving parts (102) and are used to introduce a third variable temperature medium. The third variable temperature medium can prevent the infrared window (121) from being too cold or too hot.

9. The all-quartz in-situ infrared transmission device according to claim 8, characterized in that, The all-quartz in-situ infrared transmission device also includes a first temperature-changing medium tank (310), which is made of quartz profile; the first temperature-changing medium tank (310) is disposed on the outer periphery of the joint (300) and is used to introduce a third temperature-changing medium, which can prevent the joint (300) from being too cold or too hot; wherein, the first temperature-changing medium tank (310) and the second temperature-changing medium tank (140) are connected via a temperature-changing medium passage (311) so that the third temperature-changing medium can circulate in the first temperature-changing medium tank (310) and the second temperature-changing medium tank (140).

10. The all-quartz in-situ infrared transmission device according to claim 1, characterized in that, The gas passage includes an inlet passage (231) and an outlet passage (232); the inlet passage (231) is connected to the sample area (210) to serve as an introduction channel for atmospheric gas or probe or a pressure transformation channel; the outlet passage (232) is connected to the connector (300) to serve as an outlet channel for atmospheric gas or probe or a pressure transformation channel; wherein, the gas passage includes at least two inlet passages (231), and at least two inlet passages (231) are respectively connected to the sample area (210).

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