Dissolved gas monitoring device based on surface-enhanced raman spectroscopy in a bubble column reactor

Abstract

The present invention provides a dissolved gas monitoring device based on surface-enhanced Raman spectroscopy in a bubble tower reactor, comprising: a nanostructure; a nanostructure protection part including a protective plate, a detector part, and a connection part of a bubble tower reactor coupling part; and a bubble tower reactor coupling part including a connection part of the nanostructure protection part, a bubble tower reactor connection part, and a Raman spectrometer coupling part. By overcoming the problems of nanostructure damage and signal interference caused by flow and bubbles in the bubble tower reactor, stable and highly accurate real-time monitoring of dissolved gas is possible.

Description

Technology Field

[0001] The present invention relates to a device for monitoring dissolved gas concentration based on surface-enhanced Raman spectroscopy in a bubble tower reactor. Background Technology

[0002] A bubble column reactor is a type of reactor with a bubble injection device at the bottom of a cylinder containing liquid, and is utilized in various reactions such as wet oxidation, polymerization, and fermentation. As a result, research on gas retention, bubble characteristics, flow analysis, heat and mass transfer within the bubble column reactor is actively underway, and it is also widely used in industries such as chemistry, petrochemicals, biochemistry, and metals.

[0003] To improve reaction efficiency, enhance the reactor structure, or prevent reaction failures within such bubble tower reactors, it is necessary to monitor the concentration of dissolved gases, which act as reactants, in real time. Traditionally, gas chromatography-based analytical methods have been primarily used to monitor dissolved gas concentrations in bubble tower reactors. Generally, these chromatography-based detection methods estimate the concentration of dissolved gases in the reaction solution by measuring the gaseous phase concentration and assuming equilibrium. However, because dissolved gases are consumed in real time within the reaction solution, the gas concentrations in the gaseous and liquid phases within the reactor are not in equilibrium. Consequently, indirect detection methods utilizing gas chromatography provide inaccurate concentration information. Furthermore, since gas chromatography requires continuous gas sampling, it can cause reactor contamination, and the long duration of the sampling and analysis processes makes it unsuitable for process automation.

[0004] Surface-enhanced Raman spectroscopy (SERS) is gaining attention for its high sensitivity and selectivity, as strong electromagnetic field amplification by metal nanostructures significantly amplifies Raman signals, which are the intrinsic optical signals of surrounding molecules. However, in the case of bubble tower reactors, a sparger is generally used to generate countless bubbles to improve the mass transfer efficiency of gas molecules. When these bubbles are adsorbed onto metal nanostructures, the measurement results in inaccurate findings because it measures the concentration of the gas within the bubbles rather than the concentration of the dissolved gas in the reaction solution. Furthermore, the generation of countless bubbles and the flow generated as they rise can cause damage to the metal nanostructures. Prior art literature

[0005] Korean Registered Patent No. 2208042 The problem to be solved

[0006] The objective of the present invention is to provide a device for real-time monitoring of the concentration of dissolved gas in a bubble tower reactor by overcoming the problem of signal interference caused by flow and bubbles in the bubble tower reactor. means of solving the problem

[0007] In exemplary embodiments of the present invention, a surface-enhanced Raman spectroscopy-based dissolved gas monitoring device in a bubble tank reactor is provided, comprising: a nanostructure; a nanostructure protection part including a protective plate, a detector part and a connection part of a bubble tank reactor coupling part; and a bubble tank reactor coupling part including a connection part of the nanostructure protection part, a bubble tank reactor coupling part and a Raman spectrometer coupling part. Effects of the invention

[0008] The device of the present invention can monitor dissolved gas in a bubble tower reactor in real time.

[0009] The device of the present invention has no risk of contamination of the bubble tower reactor.

[0010] The device of the present invention enables rapid and accurate concentration measurement by directly measuring the concentration of dissolved gas.

[0011] The device of the present invention does not cause problems with flow generated by bubbles and signal interference caused by bubbles within the bubble tower reactor, so the accuracy of dissolved gas monitoring is excellent.

[0012] The device of the present invention can stably monitor dissolved gas because no damage to the nanostructure is caused by the flow and bubbles generated within the bubble tower reactor. Brief explanation of the drawing

[0013] FIG. 1 is a schematic diagram of a surface-enhanced Raman spectroscopy-based dissolved gas monitoring device in a bubble tower reactor in an exemplary embodiment of the present invention. Figure 2 is a photograph of a glass substrate with a gold-palladium core-shell nanoparticle monolayer transferred in a circular shape in the center, which is used in a surface-enhanced Raman spectroscopy-based dissolved gas monitoring device in a bubble tower reactor in an embodiment of the present invention, and a scanning electron microscope image thereof. Figure 3 is a photograph of a nanostructure protection part, a bubble tower reactor coupling part, a Raman probe, and a Raman probe combined with a surface-enhanced Raman spectroscopy-based real-time monitoring device in a bubble tower reactor according to an embodiment of the present invention. Figure 4 is a photograph showing that, in an embodiment of the present invention, the protective plate of the device of the present invention prevents bubbles rising from bottom to top from approaching the detection unit within the bubble tower reactor. Figure 5 is a result showing that the concentration of dissolved carbon monoxide increased and then decreased in real time using a surface-enhanced Raman spectroscopy-based dissolved gas monitoring device in a bubble tower reactor in an embodiment of the present invention. Specific details for implementing the invention

[0014] The present invention will be described in detail below.

[0016] The present invention provides a surface-enhanced Raman spectroscopy-based dissolved gas monitoring device in a bubble tower reactor, comprising: a nanostructure; a nanostructure protection part including a protective plate, a detector part and a connection part of a bubble tower reactor coupling part; and a bubble tower reactor coupling part including a connection part of the nanostructure protection part, a bubble tower reactor connection part and a Raman spectrometer coupling part.

[0017] In this specification, nano means 100 nm or less.

[0018] The above nanostructure can perform dissolved gas monitoring of the reaction liquid in a bubble tower reactor based on surface-enhanced Raman spectroscopy.

[0019] The aforementioned surface-enhanced Raman spectroscopy refers to a high-sensitivity analysis technique for obtaining information about a material by amplifying Raman scattering signals that are difficult to detect due to weak signals, through the adsorption of the material onto a nano-sized structure.

[0020] The material of the above nanostructure may be a metal or an inorganic material.

[0021] When the material of the above nanostructure is a metal, the metal may be selected from the group consisting of gold, silver, palladium, platinum, ruthenium, rubidium, aluminum, copper, cobalt, chromium, manganese, nickel, and iron.

[0022] When the material of the above nanostructure is an inorganic material, the inorganic material may be selected from the group consisting of silicon dioxide, titanium dioxide, aluminum oxide, and silicon carbide.

[0023] The above nanostructure may be fabricated by a nanoparticle arrangement process, a deposition process, or an etching process.

[0024] The shape of the above nanostructure may be selected from the group consisting of spherical, rod-shaped, elliptical, core-shell shape, dendrimer, tetrahedron, cube, octahedron, two-dimensional triangle, and two-dimensional square.

[0025] The above nanostructure protection part may include a protective plate, a detection part, and a connection part of the bubble tower reactor coupling part.

[0026] The above protective plate functions to physically protect the nanostructure from bubbles and flow generated in the bubble tower reactor. For example, it can protect the nanostructure from bubbles rising from bottom to top within the bubble tower reactor and the resulting flow, but is not limited thereto.

[0027] The shape of the above protective plate may be a square, a rectangle, or an arc.

[0028] The above detection unit refers to a hole through which the nanostructure and the reaction liquid in the bubble tower reactor can come into contact.

[0029] The shape of the above detection unit may be a square, a rectangle, a triangle, or a circle.

[0030] The connecting portion of the above-described bubble tower reactor coupling part functions to connect the nanostructure protection part and the bubble tower reactor coupling part. For example, as shown in FIG. 1, the connecting portion of the bubble tower reactor coupling part may have internal connecting screw threads, but is not limited thereto.

[0031] In an exemplary embodiment, the connecting portion of the bubble tower reactor coupling is cylindrical, and a detection hole is present on one plane of the cylinder, and a protective plate may be attached in the height direction of the cylinder on the surface where the detection hole is present. The other plane of the cylinder is not formed with a surface, the interior of the cylinder is hollow, and a connecting screw thread is present inside the cylinder so that it can be coupled or assembled with the connecting portion of the nanostructure protective portion.

[0032] The above-described bubble tower reactor coupling part may include a connection part of the nanostructure protection part, a bubble tower reactor connection part, and a Raman spectrometer coupling part. Inside the bubble tower reactor coupling part, there is an internal space (hereinafter referred to as the central hole of the bubble tower reactor coupling part) capable of irradiating light from the Raman spectrometer onto the nanostructure.

[0033] The orientation of the hole in the detection part and the central hole in the coupling part of the bubble tower reactor must match.

[0034] The material of the nanostructure protection part or the bubble tower reactor coupling part may be a polymer, an inorganic material, or a metal.

[0035] When the material of the nanostructure protective part or the bubble tower reactor coupling part is a polymer, the polymer may be selected from the group consisting of PDMS (polydimethylsiloxane), PMMA (Polymethylmethacrylate), PET (polyethylene terephthalate), PE (Polyethylene), PP (Polypropylene), PC (polycarbonate), and hydrogel.

[0036] If the material of the nanostructure protective part or the bubble tower reactor coupling part is an inorganic material, the inorganic material may be selected from the group consisting of silicon dioxide, titanium dioxide, aluminum oxide, and silicon carbide.

[0037] When the material of the nanostructure protection part or the bubble tower reactor coupling part is metal, the metal may be selected from the group consisting of iron, cobalt, nickel, copper, titanium, chromium, or tungsten.

[0038] The connection portion of the nanostructure protection portion is combined or assembled with the connection portion of the bubble tower reactor coupling portion. For example, the connection portion of the nanostructure protection portion may be a cylindrical structure with screw threads formed on the outside, and preferably may have a nanostructure protection portion connecting screw thread as shown in FIG. 1, but is not limited thereto.

[0039] The above-mentioned bubble tower reactor connection is connected to the bubble tower reactor. For example, the above-mentioned bubble tower reactor connection may be a cylindrical structure with screw threads formed on the outside, and preferably may have screw threads for connecting the bubble tower reactor as shown in FIG. 1, but is not limited thereto.

[0040] The above Raman spectrometer coupling part functions to connect a Raman spectrometer to the device of the present invention. For example, the above Raman spectrometer coupling part may have a Raman spectrometer coupling hole as shown in FIG. 1, and the Raman spectrometer coupling hole may be a cylindrical hole, but is not limited thereto.

[0041] The above-mentioned bubble tower reactor includes, without limitation, any bubble tower reactor known in the art, provided that the apparatus of the present invention can be installed therein.

[0042] The above dissolved gas refers to a specific gas present in the reaction liquid of the bubble tower reactor.

[0043] The above dissolved gas may be H2, O2, CO2, CO, N2, or CH4.

[0044] Depending on the type of dissolved gas mentioned above, a person skilled in the art can appropriately determine the type of the nanostructure.

[0045] The device of the present invention may further include a substrate on which the nanostructure is transferred and packing disposed on both sides of the substrate.

[0046] The above substrate includes, without limitation, any substrate known in the art, provided that a nanostructure can be transferred thereto. Additionally, the nanostructure can be transferred to the substrate using any method known in the art without limitation.

[0047] The above substrate may be a transparent substrate, but is not limited thereto.

[0048] The shape of the above substrate may be circular, square, or rectangular.

[0049] The thickness of the above substrate may be 0.1 to 10 mm.

[0050] The material of the above substrate may be glass, a polymer, or an inorganic material.

[0051] When the material of the above substrate is a polymer, the polymer may be selected from the group consisting of PDMS (polydimethylsiloxane), PMMA (Polymethylmethacrylate), PET (polyethylene terephthalate), PE (Polyethylene), PP (Polypropylene), PC (polycarbonate), and hydrogel.

[0052] If the material of the above substrate is an inorganic material, the inorganic material may be selected from the group consisting of silicon dioxide, titanium dioxide, aluminum oxide, and silicon carbide.

[0053] The above packing can function to prevent leakage of the reaction liquid within the bubble tower reactor. A hole (hereinafter referred to as the central hole of the packing) is formed in the center of the packing. The orientation of the detection part hole, the central hole of the bubble tower reactor coupling part, and the central hole of the packing must be aligned.

[0054] The above packing can be placed on both sides of the substrate on which the nanostructure is transferred.

[0055] The shape of the above packing may be circular, square, or rectangular.

[0056] The material of the above packing may be rubber, but is not limited thereto.

[0058] Hereinafter, specific embodiments according to exemplary embodiments of the present invention will be described in more detail. However, the present invention is not limited to the following embodiments, and various forms of embodiments may be implemented within the scope of the appended claims. It will be understood that the following embodiments are merely intended to make the disclosure of the present invention complete and to facilitate the practice of the invention for those skilled in the art.

[0060] Examples

[0061] Preparation Example

[0062] As shown in the schematic of Figure 1, a nanostructure protective part and a bubble tower reactor coupling part were manufactured.

[0063] A nanostructure having a single layer of gold-palladium core-shell nanoparticles was prepared, and the nanostructure was transferred in a circular shape to the center of the glass substrate to produce a glass substrate with the transferred nanostructure.

[0064] Rubber packings were fitted to both sides of a glass substrate on which a nanostructure was transferred, and the device of the present invention was manufactured by positioning it inside the connection part of the bubble tower reactor coupling part and assembling the connection screw thread of the bubble tower reactor coupling part with the connection screw thread of the nanostructure protection part.

[0066] Experimental Example

[0067] 1. Confirmation of the effect of preventing contact between bubbles and nanostructures in the bubble tower reactor

[0068] When the device of the present invention was installed in a bubble tower reactor, it was confirmed whether the nanostructure inside the device of the present invention actually came into contact with the bubbles inside the bubble tower reactor.

[0069] Upon verification, it was confirmed that bubbles rising from bottom to top inside the bubble tower reactor could not come into contact with the internal nanostructure due to the protective plate of the device of the present invention (Fig. 4).

[0071] 2. Experiment on Monitoring Dissolved Carbon Monoxide Concentration in the Reaction Liquid of a Bubble Tower Reactor

[0072] Using the apparatus of the manufacturing example, the increase and decrease in the concentration of dissolved carbon monoxide in the bubble tower reactor was monitored in real time based on surface-enhanced Raman spectroscopy.

[0073] When carbon monoxide gas was injected into the bubble tower reactor, it was confirmed that the concentration of dissolved carbon monoxide in the reaction solution increased, causing the Raman signal of carbon monoxide to increase until it reached equilibrium. Subsequently, when nitrogen gas was injected into the bubble tower reactor, it was confirmed that the Raman signal of dissolved carbon monoxide decreased (Fig. 5).

[0074] Therefore, it was found that the device of the present invention can prevent bubbles generated within the bubble tower reactor from entering the nanostructure and also block flow caused by bubbles, thereby enabling stable monitoring of dissolved gases within the bubble tower reactor.

Claims

Claim 1 A dissolved gas monitoring device based on surface-enhanced Raman spectroscopy in a bubble tower reactor, comprising: a nanostructure for monitoring dissolved gas in a reaction liquid in the bubble tower reactor based on surface-enhanced Raman spectroscopy; a nanostructure protection part for protecting the nanostructure; and a bubble tower reactor coupling part connected to the bubble tower reactor; wherein one side of the nanostructure protection part and one side of the bubble tower reactor coupling part are interconnected, and the nanostructure is disposed within the interconnected space, and the nanostructure protection part includes a protection plate that protects the nanostructure from bubbles formed on the bottom surface of the bubble tower reactor. Claim 2 A surface-enhanced Raman spectroscopy-based dissolved gas monitoring device in a bubble tower reactor, wherein the coupling portion of the bubble tower reactor further comprises a Raman spectrometer coupling portion to which a Raman spectrometer is coupled. Claim 3 A surface-enhanced Raman spectroscopy-based dissolved gas monitoring device within a bubble tower reactor, wherein the bubble tower reactor coupling part has a central hole in the bubble tower reactor coupling part, which is an internal space capable of irradiating light from the Raman spectrometer to the nanostructure. Claim 4 A surface-enhanced Raman spectroscopy-based dissolved gas monitoring device in a bubble tower reactor, wherein, in claim 3, the nanostructure protection part further comprises a detector through which a Raman spectral signal from the Raman spectrometer passes, and the orientation of the detector, the nanostructure, and the central hole of the bubble tower reactor coupling part are aligned. Claim 5 A surface-enhanced Raman spectroscopy-based dissolved gas monitoring device in a bubble tower reactor, wherein, in claim 4, the nanostructure further comprises a substrate on which the nanostructure is transferred and packing disposed on both sides of the substrate, and the orientation of the detection unit, the central hole of the bubble tower reactor coupling unit, and the central hole of the packing are aligned. Claim 6 A surface-enhanced Raman spectroscopy-based dissolved gas monitoring device in a bubble tower reactor, wherein the material of the nanostructure is metal or inorganic in claim 1. Claim 7 A surface-enhanced Raman spectroscopy-based dissolved gas monitoring device in a bubble tower reactor, wherein, in claim 6, the metal is selected from the group consisting of gold, silver, palladium, platinum, ruthenium, rubidium, aluminum, copper, cobalt, chromium, manganese, nickel, and iron, or the inorganic material is selected from the group consisting of silicon dioxide, titanium dioxide, aluminum oxide, and silicon carbide. Claim 8 A surface-enhanced Raman spectroscopy-based dissolved gas monitoring device in a bubble tower reactor, wherein, in claim 1, the nanostructure is fabricated by a nanoparticle arrangement process, a deposition process, or an etching process. Claim 9 A surface-enhanced Raman spectroscopy-based dissolved gas monitoring device in a bubble tower reactor, wherein, in claim 1, the shape of the nanostructure is selected from the group consisting of spherical, rod-shaped, elliptical, core-shell shape, dendrimer, tetrahedron, cube, octahedron, two-dimensional triangle, and two-dimensional square. Claim 10 A surface-enhanced Raman spectroscopy-based dissolved gas monitoring device in a bubble tower reactor, wherein the shape of the protective plate is a square, a rectangle, or an arc in claim 1. Claim 11 A surface-enhanced Raman spectroscopy-based dissolved gas monitoring device in a bubble tower reactor, wherein the shape of the detection unit is square, rectangular, triangular, or circular. Claim 12 A surface-enhanced Raman spectroscopy-based dissolved gas monitoring device in a bubble tower reactor, wherein the material of the nanostructure protection part or the bubble tower reactor coupling part is a polymer, inorganic material, or metal. Claim 13 A surface-enhanced Raman spectroscopy-based dissolved gas monitoring device in a bubble tower reactor, wherein, in claim 12, the polymer is selected from the group consisting of PDMS (polydimethylsiloxane), PMMA (Polymethylmethacrylate), PET (polyethylene terephthalate), PE (Polyethylene), PP (Polypropylene), PC (polycarbonate) and hydrogel, the inorganic material is selected from the group consisting of silicon dioxide, titanium dioxide, aluminum oxide and silicon carbide, and the metal is selected from the group consisting of iron, cobalt, nickel, copper, titanium, chromium and tungsten. Claim 14 A surface-enhanced Raman spectroscopy-based dissolved gas monitoring device in a bubble tower reactor, wherein the dissolved gas is H2, O2, CO2, CO, N2, or CH4. Claim 15 A surface-enhanced Raman spectroscopy-based dissolved gas monitoring device in a bubble tower reactor, wherein the shape of the substrate in claim 5 is circular, square, or rectangular. Claim 16 A surface-enhanced Raman spectroscopy-based dissolved gas monitoring device in a bubble tower reactor, wherein the thickness of the substrate in claim 5 is 0.1 to 10 mm. Claim 17 A surface-enhanced Raman spectroscopy-based dissolved gas monitoring device in a bubble tower reactor, wherein the material of the substrate is glass, polymer, or inorganic material in claim 5. Claim 18 A surface-enhanced Raman spectroscopy-based dissolved gas monitoring device in a bubble tower reactor, wherein the polymer is selected from the group consisting of PDMS (polydimethylsiloxane), PMMA (Polymethylmethacrylate), PET (polyethylene terephthalate), PE (Polyethylene), PP (Polypropylene), PC (polycarbonate), and hydrogel. Claim 19 A surface-enhanced Raman spectroscopy-based dissolved gas monitoring device in a bubble tower reactor, wherein the inorganic material is selected from the group consisting of silicon dioxide, titanium dioxide, aluminum oxide, and silicon carbide. Claim 20 A surface-enhanced Raman spectroscopy-based dissolved gas monitoring device in a bubble tower reactor, wherein the shape of the packing is circular, square, or rectangular.

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