Probe for liquid analysis

Abstract

The invention relates to a probe (100) for continuous liquid analysis, comprising at least one detector (101) for measuring the spectral properties of the liquid (102) to be analyzed, and a liquid-tight housing (110) for accommodating the at least one detector (101), wherein the at least one detector (101) is accommodated in the liquid-tight housing (110), and wherein at least one window (112) is arranged in the wall (111) of the liquid-tight housing (110), through which window the at least one detector (101) detects spectral properties of the liquid (102) to be analyzed, wherein the liquid-tight housing (110) is connected to a flow channel (115) through which the liquid (102) to be analyzed flows, and wherein the at least one window (112) is directed into the flow channel (115).

Description

1 Probe for liquid analysis The invention relates to a probe for continuous liquid analysis, comprising at least one detector for measuring the spectral properties of the liquid to be analyzed and a liquid-tight housing for accommodating the at least one detector, wherein the at least one detector is housed in the liquid-tight housing, and wherein at least one window is arranged in the wall of the liquid-tight housing, through which the at least one detector detects the spectral properties of the liquid to be analyzed, wherein the liquid-tight housing is connected to a flow channel through which the liquid to be analyzed flows, and wherein the at least one window is directed into the flow channel. For continuous liquid analysis, also known as online monitoring, flow-through cuvettes are known, through which the liquid to be examined spectroscopically flows. Such flow-through cuvettes are used in laboratories or pilot plants to analyze, for example, the composition of a liquid or the concentration of a specific substance in continuous chemical processes. Flow-through cuvettes are also used in wastewater treatment to continuously monitor both untreated wastewater and purified water. A specific case is the continuous monitoring of mine water. Mine water accumulates in abandoned mines, and pumps are used to maintain it at a constant level. If the level drops, groundwater may flow into the gradually emptying mine. If the level rises too high, mine water may seep into the groundwater, introducing heavy metals from deeper rock layers. Maintaining the mine water level is a perpetual task. To ensure that groundwater does not mix with mine water, both the mine water and the surrounding groundwater are continuously analyzed. Mine water can release chlorides, heavy metals, nitrates, and pollutants from hazardous waste previously disposed of in mines to the surface. Not all of these contaminants can be continuously analyzed using spectroscopic methods, or they are only detectable with highly sensitive spectroscopic techniques, such as Raman spectroscopy. The sensitivity of the measuring instruments and the extremely harsh conditions for monitoring mine water present a significant challenge. CA 3272113 Date reçue / Received date 2025-04-292 For online monitoring of mine water using Raman spectroscopy, it is necessary to direct a laser beam into the mine water to be monitored and measure the Raman emission that is scattered back due to the Raman effect. The excitation laser light and the Raman emission differ in intensity by several orders of magnitude. Since the Raman emission has a different wavelength than the excitation wavelength, monochromatic laser scattering caused by particles can be separated from the Raman emission using diffraction gratings in the Raman spectrometer. However, stray light—such as stray sunlight that falls within the Raman emission wavelength range—cannot be separated from the actual Raman emission. Therefore, it is essential that the mine water flowing through a Raman spectrometer is protected from external light. Another problem is that a window separating the mine water from the Raman spectrometer quickly becomes covered with algae or yellowed due to precipitates from the water, eventually becoming completely opaque. Deposits may include iron oxide or other heavy metal oxides, lime deposits, and bacterial growth. The apparatus must therefore withstand the harsh conditions of a mine, guide the mine water past a window for a spectrometer while being protected from external light, and allow the window to be cleaned without damage and without requiring manual cleaning. The number of probes used in a mining area is too high to manually clean each deployed probe or Raman spectrometer within the time it takes for biofouling or deposits to form. Very similar conditions concerning biofouling and deposits are found in wastewater from agricultural operations, such as manure, wastewater from fermentation pits in biogas plants, as well as in water management, industrial and municipal wastewater treatment plants, and water circulation systems of industrial cooling towers, to name just a few examples. Such continuously monitored liquids share the characteristic of causing biofouling, bacterial growth, or the deposition of dissolved substances. These liquids are referred to in this application as substance-laden liquids. The problem of the invention is therefore to provide a probe for continuous liquid analysis that withstands the harsh conditions of substance-laden liquids, guides CA 3272113 Date reçue / Received date 2025-04-293 the substance-laden liquid past a spectrometer while being protected from external light, and is easy to clean. This problem is solved by a probe having the features as described herein. Further advantageous embodiments are specified as described herein. In some embodiments, the helical shape of the flow channel has a varying winding along its length, wherein the varying winding continuously varies. According to the gist of the invention, it is provided that the flow channel is wound. Surprisingly, it has been found that a wound shape of the flow channel, on the one hand, ensures that laser light immersed in the liquid, for example, is sufficiently re-emitted through Raman emission. On the other hand, a window facing the flow channel is protected from external light, particularly sunlight. The flow along the winding creates strong turbulence in the liquid, which slows down biofouling or the deposition of substances present in the substance-laden liquid. The probe designed in this way is suitable for various types of spectroscopic investigations. This includes all types of optical spectroscopy, such as UV / VIS spectroscopy, IR / NIR spectroscopy, light scattering measurements, polarimetry, and refractive index measurements. The probe with the wound flow channel is particularly suitable for spectroscopic online monitoring using Raman spectroscopy. To this end, an embodiment of the probe according to the invention provides that the detector is a Raman spectrometer and that a laser beam shines into the liquid to be analyzed through at least one window. A particularly suitable shape for the wound flow channel is a helical form. In addition to the helical form, other three-dimensionally wound shapes of the flow channel are possible. The exact shape of the helical flow channel can be designed in various ways. It is possible for the helical shape of the flow channel to have a varying torsion along its course, wherein the torsion continuously varies. The term "torsion" is to be understood here in the mathematical-differential geometric sense. The torsion of a helix describes its curvature and torsion. If the torsion varies, the shape is no longer a uniform helix, but rather the curvature and torsion of the helix vary. By varying the curvature, a uniform parabolic velocity profile is formed within the lumen of the flow channel. This uniformity prevents cavitation effects that would CA 3272113 Date reçue / Received date 2025-04-294 otherwise gradually erode the surface of the flow channel and a window directed into the flow channel. It also slows down biofouling and the deposition of dissolved substances. It is possible for the helical shape of the flow channel to have a constant helix diameter while the number of turns along its axis varies. In this embodiment, the liquid flowing through the flow channel undergoes an increasing number of rotations per unit time along the axis of the helix, thereby causing radial acceleration of the liquid. In another advantageous embodiment of the flow channel, the helical shape of the flow channel has both a varying number of turns along its axis and a varying helix diameter. This design enhances the effect of radial acceleration of the liquid flowing through the flow channel. The acceleration effect strongly counteracts biofouling and the deposition of dissolved substances. In yet another embodiment of the flow channel, the helical shape has a constant number of turns along its axis while the helix diameter varies, further increasing radial acceleration during inflow. In a particular embodiment of the invention, both the helix diameter and torsion may vary. This means that the helical shape of the flow channel may have both a varying number of turns along its axis and a varying helix diameter. To reliably exclude external light, the torsion of the flow channel should be at least half a turn. Thus, the helical shape of the flow channel may range from 0.5 turns (180°) to six turns (1,080°). It is possible to design more turns, but excessive turns result in high pressure losses, which hinder uniform flow through the flow channel, especially at low inflow pressures of 1 mBar to 50 mBar. For use in mine water applications, the diameter of the flow channel should not be too small to avoid excessive pressure loss and to allow for cleaning. It has been found advantageous if the flow channel has a ratio of diameter to length between 0.5% and 5%, and the diameter of the flow channel is between 2 mm and 2 cm. These values have been found optimal for the viscosity of mine water to prevent biofouling and deposits while ensuring easy flow. CA 3272113 Date reçue / Received date 2025-04-295 To clean the flow channel, a nozzle is provided, which opens into the flow channel, allowing cleaning fluid to be introduced into the flow channel. This allows the probe to be connected to a clean water hose, which regularly flushes the flow channel with clean water or a cleaning solution through the nozzle. A remotely controlled valve can trigger the cleaning process. The invention is explained in greater detail with reference to the following figures. These show: Fig. 1: A sketch of an open probe in a perspective view. Fig. 2: The open probe from Fig. 1 in a partially transparent view. Fig. 3: The open probe from Fig. 1 in a top view. Fig. 4: The open probe from Fig. 1 in a partially transparent view from another perspective. Fig. 5: Illustrations of fundamental shapes of a flow channel in the probe. In Figure 1, a sketch of an open probe 100 in a perspective view is shown. The probe 100 in this embodiment consists of a liquid-tight housing 110 that accommodates the detector 101, wherein the detector 101 is configured to measure the spectral properties of a liquid 102 to be analyzed. In the wall 111 of the liquid-tight housing 110, there is a window 112 (Fig. 2) through which the detector 101 detects the spectral properties of the liquid 102. The liquid 102 to be analyzed flows through a flow channel 115 arranged within the housing, with the aforementioned window 112 being oriented toward the liquid 102 for detection by the detector 101. The embodiment of the probe 100 shown here features exactly one detector 101. This detector is a Raman spectrometer, which directs a laser beam L through the window 112 into the liquid 102 to be analyzed and measures the spectrum of the resulting Raman scattering. However, it is also possible for more than one detector to be present in the probe 100. These detectors may share a window 112 or each have a dedicated window assigned to them. CA 3272113 Date reçue / Received date 2025-04-296 The embodiment of the probe 100 shown here is designed to be submerged in mine water for extended periods to monitor mine water quality. The problem addressed by this probe is to guide the liquid 102 past the window 112 in such a way that stray external light, such as sunlight, does not reach the detector 101, while also preventing stray laser light from the laser beam L from escaping outward. To shield against stray light, the invention provides that the flow channel 115 is wound. Due to the wound shape of the flow channel 115, the laser beam L is effectively trapped in a radiation trap, and external light, such as sunlight, cannot propagate through the windings and reach the detector. Since the probe 100 is intended to remain submerged in the liquid 102 (mine water) for extended periods, a nozzle 120 is provided, through which a cleaning fluid can be introduced into the flow channel 115. The cleaning fluid may be clear water injected under high pressure, but it is also possible to use a special cleaning fluid containing detergents or chemically active substances that dissolve contaminants, such as highly oxidizing additives like hypochlorites or peroxides. In Figure 2, the open probe from Fig. 1 is shown in a partially transparent view. In this view, the window 112 in the wall 111 of the housing 110 is visible, leading from the interior of the probe 100 to the wound flow channel 115. In addition to the window 112, the nozzle 120 is also visible, through which cleaning fluid can enter the flow channel 115. The cleaning fluid enters via the nozzle 120 and exits through openings where the liquid to be analyzed flows into and out of the probe. To illustrate the wound nature of the flow channel, Fig. 3 presents the open probe from Fig. 1 in a top view. This transparent two-dimensional representation shows the flow channel 115 as appearing to meander only in two dimensions. However, in reality, the channel is helically shaped, forming individual windings W (Fig. 5). The helical nature of the flow channel 115 is clearly evident in Figure 4. Figure 4 shows the open probe from Figure 1 in a partially transparent view from another perspective, allowing the individual windings W to be traced along the three-dimensional path of the flow channel 115. The nozzle 120 is positioned adjacent to CA 3272113 Date reçue / Received date 2025-04-297 the section of the probe 100 housing the detector 101. A cleaning hose can be connected to the nozzle 120. In Figure 5, different fundamental shapes of the flow channel 115 within the probe 100 are illustrated. Subfigure (a) shows a uniform helical flow channel. In this design, the winding pitch Δ between two windings W remains constant. The winding pitch Δ is defined as the path length along the axis A over which the winding W completes a full 360° turn. In this configuration, the diameter dH of the helix or the individual windings W remains constant, and the helix H exhibits a constant torsion in the mathematical-differential geometric sense. Subfigure (b) shows another possible configuration of a helical flow channel H. In this case, the diameter dH of the helix or the individual windings W remains constant, but the winding pitch Δ continuously varies, such that a first winding pitch Δ1 between two windings W is greater than a second winding pitch Δ2 between another pair of windings W. The change in winding pitch of the helix H occurs continuously in the mathematical-differential geometric sense and does not exhibit abrupt changes. Subfigure (c) shows another possible configuration of a helical flow channel H. Here, the diameter dH of the helix or the successive windings is not constant, but instead passes through a minimum. However, the winding pitch Δ remains constant, meaning that the distance between successive windings W remains unchanged. The variation in the diameter dH of the helix or successive windings occurs continuously and does not exhibit abrupt transitions. Subfigure (d) illustrates yet another possible configuration of a helical flow channel H. In this case, neither the diameter dH of the helix or the individual windings W is constant, nor is the winding pitch Δ uniform. Instead, a first winding pitch Δ1 between two windings W is greater than a second winding pitch Δ2 between another pair of windings W. CA 3272113 Date reçue / Received date 2025-04-298 R E F E R E N C E L I S T 100 Probe 101 Detector 102 Liquid 110 Housing 111 Wall 112 Window 115 Flow channel 120 Nozzle A Axis dH diameter (helix) dS diameter (flow channel) D Winding pitch D1 Winding pitch D2 Winding pitch L Laser beam W Winding CA 3272113 Date reçue / Received date 2025-04-29

Claims

9 What is claimed is:

1. Probe for continuous liquid analysis, comprising: at least one detector for measuring the spectral properties of the liquid to be analyzed, and a liquid-tight housing for accommodating the at least one detector, wherein the at least one detector is housed in the liquid-tight housing, and wherein at least one window is arranged in the wall of the liquid-tight housing, through which the at least one detector detects spectral properties of the liquid to be analyzed, wherein the liquid-tight housing is connected to a flow channel, through which the liquid to be analyzed flows, wherein the at least one window is directed into the flow channel, wherein the flow channel is wound, wherein the flow channel has a helical shape, and wherein the helical shape of the flow channel has both a varying number of turns along its axis and a varying diameter of the helix.

2. Probe according to claim 1, wherein the detector is a Raman spectrometer and that a laser beam shines into the liquid to be analyzed through at least one window.

3. Probe according to claim 1 or 2, wherein the helical shape of the flow channel has a varying winding along its length, wherein the varying winding continuously varies. CA 3272113 Date reçue / Received date 2025-04-2910 4. Probe according to claim 1 or 2, wherein the helical shape of the flow channel has a constant diameter of the helix with a varying number of turns along its axis.

5. Probe according to claim 1 or 2, wherein the helical shape of the flow channel has a constant number of turns along its axis with a varying diameter of the helix.

6. Probe according to claim 1 or 2, wherein the helical shape of the flow channel comprises between 0.5 turns (180°) and six turns (1,080°).

7. Probe according to any one of claims 1 to 6, wherein the flow channel has a ratio of the diameter of the flow channel to its length between 0.5% and 5%, and the diameter of the flow channel is between 2 mm and 2 cm.

8. Probe according to any one of claims 1 to 6, wherein a nozzle opens into the flow channel, through which cleaning liquid can flow into the flow channel. CA 3272113 Date reçue / Received date 2025-04-29