The present invention relates to a device for analyzing a product to be analyzed that is located in a product space.
To increase the flexibility and efficiency of industrial production processes, a comprehensive understanding of processes is necessary. Sensors providing information about material compositions, process parameters, reaction processes and product qualities are required.
Distinct advantages are provided here by optical spectroscopic sensors, which function without media contact. The most commonly used technique is spectroscopy in the near-infrared region (NIR) within the wavelength range of 0.8-2.5 μm. An extension of such spectroscopic analysis methods into the mid-infrared region (MIR) with wavelengths of 3-30 μm provides high sensitivity and selectivity. Liquid water in particular and thus all aqueous solutions absorb very strongly in the MIR region, meaning that very small layer thicknesses less than 100 μm must be used for transmission measurements. A promising method that is already known is the use of attenuated total reflection, or ATR for short.
The ATR analysis method is already widespread for testing liquids and solids in process analytics. This means that it is possible to test strongly absorbing samples spectroscopically. The customary arrangement of a so-called ATR probe is formed of an ATR crystal with planar interfaces, of which at least one is contacted with the medium to be analyzed. An electromagnetic wave totally reflected inside the crystal at the interface to the medium is attenuated owing to the interaction of its evanescent field with the medium to be analyzed in the outer region of the crystal. What can then be analyzed is the possibly spectrally resolved degree of attenuation, which is linked to the material properties of the medium to be analyzed. In the case of customary ATR instruments in the UV to MIR radiation range, light sources with a broad spectral band are predominantly used. Here, detection is achieved using spectrometers or individual detectors with spectral filters.
In ATR spectroscopy, the penetration depth of the evanescent wave into the medium is only about one wavelength. In other words, in the NIR region, only a layer thickness of distinctly less than 1 μm is analyzed using ATR technology, whereas several micrometers can be reached with MIR spectroscopy owing to the larger wavelength of several micrometers. In general, contaminants on the surface is a certain problem in ATR spectroscopy, irrespective of the stated spectral region. Coverings on the surface result in the sensor becoming “blind”. An ATR spectrometer or ATR photometer must therefore always have clean and easily cleanable surfaces.
Customary ATR arrangements use crystals having planar surfaces, such as prisms for example, as ATR elements. A particular challenge is the integration of such prisms or even plates in process probes. The probe bodies are usually designed with a cylindrical probe shaft for introduction into a reactor or a pipeline via an opening as a flange. The ATR elements are then situated either at the tip of the probe shaft or on the longitudinal side. In the case of an ATR element at the tip, the number of reflections and thus the sensitivity is, however, limited.
The international published specification WO 2015/052893 A1 shows an arrangement in which the light is coupled into a cylindrical ATR element from the end faces of the cylinder and passes through the ATR element longitudinally in a spiral manner. However, the incorporation of the ATR element in holders gives rise to edges and projections on which deposits can form. Cleaning the edges and projections with cleaning liquids, with hot steam or mechanical means is then accordingly complicated.
Furthermore, the publication WO 2007/009522 A1 from the area of NIR process spectroscopy discloses an arrangement for reflection measurement. In operation, light is guided into the process medium laterally to the probe body through a window and the back-scattered or reflected light is likewise laterally detected. The described arrangement can be cleaned very easily.
It is therefore an object of the present invention to provide a device which can be used optimally for analysis and allows simple cleaning.
An exemplary embodiment of the invention provides a device for the analysis of a product to be analyzed that is situated in a product space, comprising a probe body with a circumferential wall that is arranged in a probe housing, comprising at least one radiation source and at least one optical receiver, comprising at least one measurement window in the probe body with an entrance region and an exit region for measurement radiation, and comprising an evaluation unit. The probe body can be brought to a measurement position at which at least one part of the probe body in which the measurement window is situated plunges through an opening of the probe housing into the product space for analysis. Furthermore, the probe body can be brought to a retracted position at which the probe body is at least still partly situated in the region of the opening of the probe housing and covers the opening at the same time. According to the achievement according to the invention, the at least one measurement window is an ATR element, the ATR element being arranged in at least one subregion of the circumferential wall of the probe body in the beam path.
The invention consequently provides an analysis device which can be used to test products of differing nature that are primarily situated on the outer side of the probe body.
Here, one or more ATR elements can be constructively adapted to the geometry of the probe body. If the probe body has substantially a hollow-cylinder geometry in the region of the at least one ATR measurement window, an ATR element is adapted to the specified conditions and integrated in the probe body without protruding edges. As a result, the probe body is realized in a particularly compact manner and thus, in particular, in an easily cleanable manner.
In principle, testing of a medium to be analyzed on the inner side of the probe body is also envisaged. In the case of such use as pipe probe, process medium flows though the inside of the probe. Owing to the smooth inner surfaces, it is possible for chemomechanical cleaning to be carried out here like in other parts of the process plant without removing parts of the analysis probe.
The measurement radiation used can arrive at the ATR element by means of suitable optical aids, for example prisms or mirrors. In one configuration of the invention, the measurement radiation used for analysis can also be guided to the ATR element by means of transmission and receiving light guides and, from there, to the optical receiver. The measurement radiation enters the ATR element such that it is totally reflected within the ATR element and, in this way, passes inside through the ATR element in order to interact via its evanescent field with the product to be analyzed. The measurement radiation resulting from the ATR element due to interaction is, for example, guided back to the optical receiver by means of a receiving light guide and further processed by the evaluation unit. Here, a high number of reflections of the measurement radiation in the ATR element achieves a correspondingly high sensitivity of the arrangement.
In the measurement position, the probe body can plunge, at least in part with the ATR element as measurement window, through an opening of the probe housing into the product space for analysis. In the case of suitably curved embodiments of the ATR element, it is, for example, possible to achieve a high number of reflections in a small space via the whispering gallery effect in order to boost the measurement signal. The probe body can be introduced into the process via the opening as an access flange and thus has contact with the process medium on the outer side.
Once the probe body is situated in a retracted position at which it is at least still partly situated in the region of the opening of the probe housing, but the ATR element is arranged outside the product space, said ATR element can be cleaned easily. Options for the cleaning procedure are, for example, already described in WO 2007/009522 A1, which corresponds to U.S. Pat. No. 7,869,028, which is incorporated herein by reference.
Suitable materials for ATR elements are, for example, sapphire, Ge, ZnSe, ZnS, CaF2, BaF2, chalcogenide glasses or diamond. As ATR element for the MIR spectral region, preference is given to using the material sapphire, which has an excellent process reliability, up to a wavelength of about 5 μm. For larger wavelengths, it is possible to use materials such as germanium, ZnSe, ZnS, CaF2, BaF2, chalcogenide glasses or diamond. The probe body can, for example, be formed of stainless steel. Hard materials, such as, for example, diamond or diamond-like carbon, can also be taken into consideration as surface coatings. In particular, at least where the surface of the probe body comes into contact with the product to be analyzed. This serves to increase the abrasion resistance, both in the cleaning process and when plunging the probe body into firm substances.
An advantage of the invention is that the constructive solution of the probe body is realized in a favorable manner, both for optical considerations and for fluidic considerations with regard to possible soiling and cleanability of the probe body. As a result of the integration of an ATR element fitted geometrically into the probe body without corners and edges, it is possible for cleaning to be carried out easily. In addition, there is good flow around the probe surface when process media are moved, and, as a result, a rapid material exchange on the surface is ensured.
For instance, the analysis device according to the invention is particularly suitable for in-line process analytics in the chemical and pharmaceutical industry and in the food industry, for example for the determination of the alcohol or sugar content in beverages or of the composition of cooking oils and fats. Similarly, the analysis device is suited to analyses in the area of the petrochemical and oil industry for the determination of the composition and aging of fuels and lubricants. Usage in biotechnology can serve for the monitoring of biogas reactors in fermentation processes. The improved process analytics according to the invention allow higher plant efficiencies and consistently higher product qualities.
In an advantageous configuration of the invention, the ATR element can be designed as a hollow cylinder or hollow sphere. Thus, the measurement radiation in the ATR cylinder can be guided over the circumference by multiple reflections. The coupling-in and coupling-out of light is preferably achieved on the inner side of the hollow cylinder or the hollow sphere or from the end faces of the hollow cylinder or the hollow sphere. A configuration as hollow-cylinder segment or as hollow-sphere segment is conceivable too.
Here, it is possible in particular to fit a cylindrical ATR element without edges in a smooth manner into an often likewise cylindrical probe body of a process probe. The cylindrical arrangement allows, firstly, a good flow around the sensitive surface during the process and also an efficient cleaning. Secondly, the stated geometries can achieve a high number of reflections and thus a high sensitivity.
In a further variant of the invention, the entrance region and/or exit region of the measurement radiation can, in the case of a cylindrical ATR element, be designed such that the measurement radiation in the ATR element is guided in a spiral and circumferential manner to the exit region. Owing to a spiral light propagation, it is possible to further extend the light path. The number of reflections is specified, firstly, by the height of the cylinder element and, secondly, by the slope of a screw thread.
Alternatively, the entrance region and/or exit region of the measurement radiation can advantageously, in the case of a cylindrical ATR element, be designed such that the measurement radiation in the ATR element is guided in a circular and circumferential manner to the exit region. In this embodiment, the coupling-in of light can, in addition to further embodiments, also be advantageously realized by a wedge-shaped notch along the inner side of the cylinder or by lattice structures in the longitudinal direction. In this arrangement, a good illumination of the cylinder is possible from the inner side of the cylinder via cylinder optics for the coupling-in and coupling-out of light.
In a further advantageous configuration of the invention, multiple ATR elements arranged with distribution over the circumferential wall of the probe body can be provided. Multiple ATR elements can be developed in various ways and, for example, combined with other optical measurement methods.
In a further additional embodiment, the at least one ATR element can be designed as a cylinder segment. Also possible are arrangements comprising more than two longitudinal cylinder segments. A cylinder segment can be fitted optimally into a likewise cylindrical probe body. If the coupling-in elements for the measurement radiation are realized as grooves or other notches or else as coupling-in lattices in the ATR element, there are no projecting corners or edges in the coupling-in and coupling-out region.
Advantageously, the at least one ATR element can be designed as a half shell. In a preferred embodiment, two cylinder shells are used instead of a continuous cylindrical ATR element in the form of a pipe. The coupling-in of the light can be realized in this case either from the end face or from the longitudinal side through appropriate abrasion or via lattice couplers. In an ATR element, the coupling-in of light and coupling-out of light can, for example, also be realized in every embodiment by tapered abrasion on the end faces of the pipe.
For example, the at least one ATR element can be flush with the outer side of the circumferential wall of the probe body. This makes it possible to easily clean any possible soiling on the outer side.
The at least one ATR element can, apart from the entrance region and/or exit region of the measurement radiation, be flush with the inner side of the circumferential wall of the probe body. In the case of specific probe types, there can be, on the inner side too, soiled inner surfaces which must be cleaned. Moreover, owing to smooth inner surfaces, the structural space is better accessible for beam-guiding elements.
Advantageously, the entrance region and/or exit region of the measurement radiation of an ATR element can be designed such that the measurement radiation in the ATR element is guided to the exit region in parallel to the longitudinal axis. Self-evidently, the measurement beam in the ATR element is reflected multiple times and, as a result, also runs in a zigzag manner. A parallel guidance of the measurement radiation relative to the longitudinal axis of an ATR element forms the basis of an axis-parallel linear propagation from the entrance region right up to the exit region.
The entrance region and/or exit region of the measurement radiation of the ATR element can be designed as a lattice coupler and/or as a prism coupler. In ATR technology, it is consequently possible to conceive not only prism coupling, but also lattice coupling. Lattice coupling can be realized on the inner side or outer side of the ATR element by the introduction of usually annular lattice structures. Said lattice structures on the inner side of the ATR element can also be structured through the wall of the ATR cylinder, for example via a chemical etching process, mechanically, or by a laser process.
Furthermore, the entrance region and/or exit region of the measurement radiation of the ATR element can preferably be designed as a notch or in a tapered realization on the inner side of the ATR element. As a result, no projecting corners or edges are generated, especially on the inner surface of a probe housing in the transition region of the ATR element.
Advantageously, the at least one ATR element can be usable for the coupling-in and coupling-out of further optical measurement arrangements. Here, with exposure and detection from the inner side, the ATR measurement method can be combined with reflection spectroscopy or other spectroscopy methods in the same measurement probe, with, for example, a hollow cylinder or a segment also serving as optical element for these methods. What are particularly advantageous are embodiments which provide not only the coupling-in and coupling-out of light for the ATR element, but also light sources and detection mechanisms for optical imaging, reflection, scattering and/or Raman spectroscopy measurements. These measurements can be carried out simultaneously with the ATR measurement.
For example, a UV/VIS/NIR or MIR reflection measurement or a scattered-light measurement can be carried out simultaneously or alternatingly with the ATR measurement. Said measurement can either be done with the same light source or be run with an entirely different light source. In the case of radiation through the ATR element in the perpendicular direction, it is possible to easily identify soilings on the surface of the cylindrical material. This means that it is possible to ascertain a reliable and accurate value for the functionality of the probe. In the case of use of an imaging method, for example with a CCD camera, it is possible to provide information about inhomogeneous distributions in the liquid process medium or about coverings on the ATR element in relation to gas bubbles or particles, which can be correlated with the ATR measurements. In the case of use of Raman spectroscopy, it is possible to use a laser as light source. Designing the ATR element as cylinder lens can in this case improve the optical collection efficiency, especially for the weak Raman effect.
In this case, the combination of multiple technologies provides information about the composition of a liquid medium, by means of ATR technology, and about the properties of particles or gas bubbles present in the medium, by means of light scattering or diffuse reflection measurement. Beyond this, a check for possible soiling of the ATR surface is also possible, which can, for example, be used to control a cleaning system.
The at least one ATR element can be realized as an imaging optical element for further optical measurement arrangements. The ATR element can in this case also be used as a lens for the other measurement methods, especially for further optical process sensor systems. Advantageously, the ATR element can also be designed in the shape of a lens or torus on the inner side. A lens form of the ATR element can additionally achieve an improvement in sensitivity for these sensor systems.
Furthermore, the at least one ATR element can be at least partly coated with a dielectric layer and/or with a metal layer on the inner side and/or outer side. In this case, one part of the pipe can also be coated with metal to improve coupling-in, in order to serve as reflector.
Because there are devices or components by means of which the measurement radiation can, after exit from the ATR element, be coupled again into said ATR element, it is possible to achieve a contrast enhancement in the measurement. Alternatively or additionally, the area of use of the device according to the invention can be extended in that there are devices or components for the simultaneous coupling-in of measurement radiation into the ATR element at different points.
Further scope of applicability of the present invention will become apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
The present invention will become more fully understood from the detailed description given hereinbelow and the accompanying drawings which are given by way of illustration only, and thus, are not limitive of the present invention, and wherein:
For simplification of the representation,
The light can be coupled either into the entire cylinder or into a segment of the cylinder and coupled out. A homogeneous coupling-in and coupling-out over the entire circumference of the cylinder is possible, for example with the aid of so-called Schwarzschild or Cassegrain optics or via IR LED ring illuminations from the inner side.
In the embodiment according to
The light can be fed in with optical fibers on the inner side and, after passage through the ATR element 6, coupled out via optical fibers. The other end of the optical fibers is situated in the evaluation unit 7, depicted in
A pivoted or switchable design of the mirror 70 can allow a change in contrast by a factor of two, since this makes it possible to double or halve the number of total reflections of the radiation at the interface of the ATR element 6.
The parallelized input radiation shown can be achieved in a wide variety of different ways, especially by means of a faceted, mirrored element, all-round mirror, an arrangement of individual mirrors or the like.
The bevels 69 and 69′ depicted in
The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are to be included within the scope of the following claims.
Number | Date | Country | Kind |
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102015122995.1 | Dec 2015 | DE | national |
This nonprovisional application is a continuation of International Application No. PCT/EP2016/082520, which was filed on Dec. 23, 2016, and which claims priority to German Patent Application No. 10 2015 122 995.1, which was filed in Germany on Dec. 30, 2015, and which are both herein incorporated by reference.
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Number | Date | Country | |
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20180306726 A1 | Oct 2018 | US |
Number | Date | Country | |
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Parent | PCT/EP2016/082520 | Dec 2016 | US |
Child | 16025520 | US |