EP3494383A1 - Dispositif d'identification de substances - Google Patents

Dispositif d'identification de substances

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Publication number
EP3494383A1
EP3494383A1 EP17761795.8A EP17761795A EP3494383A1 EP 3494383 A1 EP3494383 A1 EP 3494383A1 EP 17761795 A EP17761795 A EP 17761795A EP 3494383 A1 EP3494383 A1 EP 3494383A1
Authority
EP
European Patent Office
Prior art keywords
light
fluorescence
sample
identification result
substance
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP17761795.8A
Other languages
German (de)
English (en)
Inventor
Dirk Fey
Juergen Bohleber
Thomas Bohe
Gunther Krieg
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of EP3494383A1 publication Critical patent/EP3494383A1/fr
Pending legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/645—Specially adapted constructive features of fluorimeters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B07—SEPARATING SOLIDS FROM SOLIDS; SORTING
    • B07C—POSTAL SORTING; SORTING INDIVIDUAL ARTICLES, OR BULK MATERIAL FIT TO BE SORTED PIECE-MEAL, e.g. BY PICKING
    • B07C5/00—Sorting according to a characteristic or feature of the articles or material being sorted, e.g. by control effected by devices which detect or measure such characteristic or feature; Sorting by manually actuated devices, e.g. switches
    • B07C5/34—Sorting according to other particular properties
    • B07C5/342—Sorting according to other particular properties according to optical properties, e.g. colour
    • B07C5/3425—Sorting according to other particular properties according to optical properties, e.g. colour of granular material, e.g. ore particles, grain
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6408—Fluorescence; Phosphorescence with measurement of decay time, time resolved fluorescence
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/84—Systems specially adapted for particular applications
    • G01N21/85—Investigating moving fluids or granular solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • B29B2017/0213—Specific separating techniques
    • B29B2017/0279—Optical identification, e.g. cameras or spectroscopy
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N2021/6417—Spectrofluorimetric devices
    • G01N2021/6421—Measuring at two or more wavelengths
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/84—Systems specially adapted for particular applications
    • G01N21/85—Investigating moving fluids or granular solids
    • G01N2021/8592—Grain or other flowing solid samples
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65—Raman scattering
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2201/00—Features of devices classified in G01N21/00
    • G01N2201/06—Illumination; Optics
    • G01N2201/069—Supply of sources
    • G01N2201/0696—Pulsed
    • G01N2201/0697—Pulsed lasers
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/44—Resins; Plastics; Rubber; Leather
    • G01N33/442—Resins; Plastics
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the invention relates to a device for identifying one or more substances in a material, in particular wherein the material is in granular form, comprising at least one light source, preferably in the form of a laser, for irradiating a sample of the material with light of at least one wavelength, a detector for Detecting the re-emitted light from the sample and an analyzer for spectroscopic analysis of the detected light.
  • the invention further relates to a method for the identification of one or more substances in a material, in particular wherein the material is in granular form, wherein at least one light source, preferably in the form of a laser, a sample of the material is irradiated with light of at least one wavelength and by means a detector, the light re-emitted from the sample of the material is detected and the detected light is spectroscopically analyzed by an analyzer.
  • at least one light source preferably in the form of a laser
  • a sample of the material is irradiated with light of at least one wavelength and by means a detector, the light re-emitted from the sample of the material is detected and the detected light is spectroscopically analyzed by an analyzer.
  • plastic recycling which converts existing substances, which are substances that have been processed in products and are no longer needed, into valuable substances, ie substances that are suitable for reprocessing in products. This can then be spared the resources required for the production of the respective substances.
  • the control of product quality or color is an essential quality criterion in numerous technical processes.
  • plastic containers particularly plastic containers for the beverage industry using granular recycled material
  • the separation and sorting of different color fractions different types of plastics, e.g. Polyethylene, polyamide, polyvinyl chloride, nylon, silicone, etc.
  • the detection and sorting of, for example, with gasoline, diesel, benzene, toluene, xylene, etc. contaminated fragments required to enable re-use in the food industry.
  • the recyclable pure base materials must be able to be distinguished and separated from contaminated materials or substances.
  • it is desirable if differently colored fragments can also be sorted into pure color fractions.
  • plastics are mixed with certain flame retardants to prevent ignition. These are used, inter alia, in the field of electronic devices or in automobiles in order to prevent or at least slow down or inhibit inflammation. Due to their partial persistence and tendency to bioaccumulate they are increasingly displaced by other less problematic flame retardants. Ultimately, however, these are still found in old appliances and must therefore be taken into account, at least when recycling.
  • DE 43 12 915 A1 shows a device for sorted separation of plastics by means of IR spectroscopy. This has However, the disadvantage that with black-colored plastics they can not be selectively detected with this technique and therefore can not be separated according to type.
  • WO 98/19800 discloses a system for sorting a large number of polymers from secondary raw materials by using Raman spectroscopy.
  • Raman spectroscopy is characterized by very low intensities of the spectra compared to other spectroscopic methods, it is useful for large scale application, i. the identification of several tons of substances per hour, not suitable.
  • a further object of the present invention is, in particular chemically similar material added with additives, reliable differ.
  • it is an object of the present invention to provide a method and apparatus that is easy to implement and that further analyzes and identifies mass flows of material produced during recycling.
  • Another object of the present invention is to provide an alternative method and apparatus for identifying substances in and / or on a material.
  • the present invention solves the above objects in a device for identifying one or more substances in a material, in particular wherein the material is in granular form, comprising at least one light source, preferably in the form of a laser, for irradiating a sample of the material with light of at least one Wavelength, a detector for detecting the re-emitted from the sample and / or transmitted through the sample light and an analysis device for spectroscopic analysis of the detected light, characterized in that the analysis device cooperates with the detector and they are designed to
  • the at least one substance is at least partially identified.
  • the present invention solves the above objects in a method for the identification of one or more substances in a material, in particular wherein the material is in granular form, wherein with at least one light source, preferably in the form of a laser, a sample of the material is irradiated with light of at least one wavelength and by means of a detector re-emitted from the sample of the material and / or transmitted through the sample light is detected and the detected light is analyzed spectroscopically by an analyzer, characterized in that
  • the detected light is analyzed and a first identification result for at least one substance of the sample is created and wherein in the case of a non-unique first identification result, a second identification result for the at least one substance based on a
  • the abovementioned objects are achieved by using the fluorescent light decay time for checking, in particular merely plausibility, a substance of a material which is at least partially identified by U VA / IS spectroscopy and / or fluorescence spectroscopy and / or Raman spectroscopy ,
  • the identified substances can be checked here by quantitative use of the fluorescent light decay time, in particular also only with regard to plausibility.
  • a further advantage is that a simple, in particular modular implementation with simultaneous reliable evaluation and thus also reliable identification is made possible.
  • Another advantage is that chemically similar substances and / or their additives can be reliably distinguished and identified.
  • Another advantage is that even non-plastics such as rubber, wood or the like can be identified and then optionally also be separated.
  • an advantage is that particular Flame retardants, which are admixed as additives, such as plastics, can be reliably identified.
  • an identification of substances, their additives and / or their properties, such as color, etc. allows. It is thus also possible to determine only the additive or the additives or only the type of substance or only the color of the substance. It is thus also possible, in particular, to determine both the substances and partially dissolved additives present in the substances as well as the respective color.
  • substrate is to be understood in particular in the claims, preferably in the description of any type of solid, liquid or gaseous substance.
  • fabric means any type of polymer or polymer, for example
  • silicone or silicone polymer in particular silicon tectosilane granulate, silicone tectosil film, silicone adhesive Sn, silicone adhesive Pt, any type of silicone hose, etc.
  • PE any type of polyethylene PE, such as LDPE, HDPE and UHDPE,
  • additive is to be understood in particular in the claims, preferably in the description, any intentional or undesired additions to a substance or substances, in particular flame retardants, preferably halogenated, in particular brominated and / or chlorinated flame retardants, for example comprising
  • Measurement signal is to be understood in particular in the claims, preferably in the description, a variable that has been detected, for example, by means of a sensor and is provided by the sensor in another form, if necessary, for forwarding or processing
  • Measurement signal is understood to mean both the unchanged signal directly received by the sensor ("raw signal”) and a modified, further processed and / or processed signal.
  • sample is to be understood in particular in the claims, preferably in the description, in particular the entirety of the material to be examined, for example, the plastic, in the form of bottles, flakes, granules, etc. and optionally with existing additives ,
  • fluorescence decay time in particular in the claims, preferably in the description also the term “fluorescence lifetime”, “fluorescence lifetime constant”, “fluorescence decay time constant”, or the like. Understood.
  • multi-exponential multi-exponential
  • higher-exponential are understood in particular in the claims, preferably in the description “bi-exponential”, and / or “tri-exponential”, etc.
  • the term "partial” in relation to the identification of a substance means that, for example, only the nature of the substance is determined but not its exact chemical formula, for example, a partial identification of a substance is "plastic” but not "PE “or” PVC ".
  • the at least one light source is designed to emit at least two wavelengths.
  • the sample can be irradiated with different wavelengths, which not only increases the number of possible substances to be identified, but also allows a more accurate identification based on the first and the second identification result.
  • the at least two wavelengths can be generated based on a fundamental frequency and their frequency doubling and / or their frequency trimming and / or quadrupling.
  • a material sample can be irradiated with UV light and with visual light so that a more precise first identification result can be obtained on the basis of these two wavelengths and / or a more precise identification of the substance (s) and optionally its additive or additives is made possible on the basis of the first and second identification result.
  • a frequency multiplication ie each multiplication of a frequency with an integer, can be used to generate the at least two wavelengths.
  • At least one of the at least two wavelengths lies in the range between 233 nm and 300 nm, in particular between 250 nm and 280 nm, preferably 266 nm, the at least one other wavelength being the corresponding wavelength doubling of the one wavelength.
  • these can be at least two wavelengths, for example, the wavelengths of 1064 nm, 532 nm, 354 nm and / or 266 nm.
  • the sample is irradiable in a first direction and the re-emitted light is detectable in a second direction, wherein the first direction and the second direction are substantially opposite. In this way, a particularly compact design of the device as a whole is made possible. If the sample is transparent to the relevant wavelength (s), it may alternatively or additionally be measured in terms of absorption or transmission.
  • the first identification result can be checked for plausibility by the analysis device on the basis of the second identification result ascertained by means of the FLZA.
  • the at least one light source is a pulsed light source with pulse durations of more than 1 ns and less than 1 ms, preferably more than 1 ns and less than 100ns, in particular more than 1 ns and less than 10ns, preferably between 5ns and 10ns.
  • a repeated measurement of the substance for its identification take place, so that several suggestions, ie irradiations and several detections are made possible in a row.
  • the pulse duration of the at least one light source is adapted to the time recording of the re-emitted and / or transmitted light in such a way that the distance between the light pulses essentially corresponds to the detection time of the re-emitted and / or transmitted light by the detector. This makes it possible to carry out several measurements one after the other in an extremely efficient manner, so that overall the identification of the substance takes place in a particularly reliable manner.
  • the re-emitted and / or transmitted light can be detected in the nanosecond range by means of the detector. This is by means of the detector a temporally high-resolution detection of the light possible.
  • a transport device for supplying and discharging the sample is arranged.
  • the sample can be easily fed to an identification.
  • the detector is designed to subdivide a recorded spectrum into relevant and non-relevant areas for the later analysis, to reject the non-relevant areas and to insert FLZA-relevant data into the spectrum instead of the non-relevant areas.
  • the spectrum may be represented or stored by 32 or 64 individual values in a memory of a memory device. Play the Togethers St. End values not matter, so for example the 64th value, the detected fluorescence decay time is stored instead of this value. This saves storage space.
  • the multiple-exponential fluorescence decay time constants can be determined and analyzed by means of the FLZA, in particular can be analyzed in a multi-exponential manner.
  • bi-exponential or tri-exponential fluorescence decay time constants it is possible to more easily and safely detect, for example, the plastic and / or its additive or additives.
  • even special batches e.g. can be reliably identified with silicone dehives or special processing forms.
  • those with oils or other lipophilic substances e.g. Otto fuel, diesel fuel and lubricating oils as an additive contaminated plastic and its additive (s) are also reliably identified.
  • a measurement signal of the detected light output by means of the detector is integrated over at least a specific period of time for determining the fluorescence decay time constant by the analysis device, and in particular averaged.
  • the electronic outlay for the detection and analysis device can be made more favorable.
  • a reliable determination of the fluorescence decay time constant is made possible.
  • the measurement signal is integrated over a plurality of, in particular non-overlapping, time periods by means of the analysis device. This significantly increases the reliability of determining the fluorescence decay time constant.
  • the two time periods are the same in duration, different in terms of their limits.
  • the time intervals for the FLZA can be provided in a simple and reliable manner.
  • the analysis device can be connected or connected to a memory device and wherein the analysis device comprises at least one integrator, wherein the measurement signal is integrated separately over two non-overlapping time periods by means of the at least one integrator and wherein the values for the integrated signals are related to each other and based this relation of the at least one substance can be identified on the basis of reference reference values stored in the memory device. Relation is to be understood here in particular in the mathematical sense and can in particular consist of a quoting of the two measured integrated components of the fluorescence decay time constant. On the basis of the quotient thus obtained, it can be compared, for example, with corresponding reference quotients stored in the storage device, and thus a substance and / or its additives can be determined.
  • the at least one time period corresponds to a falling edge of the measurement signal.
  • the position of at least one time period before and / or after a usual half-life of a fluorescence lifetime can be selected. As a result, the signal-to-noise ratio can be significantly improved since the re-emitted light of the measured sample can be used more effectively.
  • the fluorescence decay time constant of the at least one substance to be detected is roughly known or ascertainable and the duration of the light pulses is smaller than the roughly known fluorescence decay time constant, in particular at least a factor of 5, preferably at least a factor of 10.
  • the duration of the light pulses can be less than 1 ms, preferably less than 100 ns, in particular less than 10 ns, preferably between 5 ns and 10 ns. It can thus be achieved that the duration of the excitation pulse can be selected to be considerably smaller than the fluorescence lifetime.
  • Such light pulses can be generated efficiently with semiconductor lasers.
  • a sorting device is arranged for the separation of identified substances from a material flow of substances. This is a simple and reliable way of separating possible, for example, contaminated plastics.
  • an optical grating is arranged in a detection beam path of the re-emitted and / or transmitted light and the light diffracted by the optical grating in zeroth or first order is used for FLZA, in particular for determining the fluorescence decay time constant. In addition to the determination of the fluorescence decay time constant, it is thus also possible to carry out further identification processes in a simple manner, for example by means of light in a higher order.
  • the light is used, for example, in zero order to the FLZA, for example, the light in the first order to the optical path for optical spectroscopy, for example.
  • To an array of 32 photomultipliers for Detection are then passed, since its light path or beam path is then not blocked by a corresponding detector for the FLZA.
  • the sample can be irradiated several times in succession with light of at least one wavelength, and the correspondingly re-emitted and / or transmitted light can be repeatedly measured and analyzed. This further increases the reliability, especially in the determination of the fluorescence lifetime constant, since different measurements can serve as a basis for spectroscopic analysis as well as for FLZA.
  • the at least two periods of time to different temporally different, in particular successive, irradiation of the sample with light can be assigned bar.
  • One of the advantages achieved with this is that the requirements for the electronic components for the evaluation are thereby further reduced, since excitation and measurement are excited and measured in different cycles. It is therefore irradiated and measured at different times.
  • the detection of the re-emitted and / or transmitted light by means of the detector by the irradiation of the sample with light can be triggered.
  • a time-shifted and triggered by the excitation light pulse measurement can be made so that a measurement within a fluorescence decaying process is made possible, especially with periodic excitation.
  • FIG. 1 in schematic form an apparatus according to an embodiment of the present invention
  • FIG. 2 in schematic form parts of a method according to a
  • FIG. 3 in schematic form parts of a device according to a
  • Fig. 7 shows a measurement of a fluorescence decay time constant of polystyrene
  • Fig. 8 shows a measurement of a sample of high impact polystyrene.
  • Fig. 1 shows in diagrammatic form a device according to an embodiment of the present invention
  • Fig. 2 shows in schematic form parts of a method according to an embodiment of the present invention.
  • device 1 pulsed light source 2, sample 3, filter 4, lens 5, sensor 6, signal conditioning 7, differentiator 8, trigger generation 9, retarder 10, timing element integrator 1 1a, 11b, integrator 12a, 12b, quotation 13, evaluation 14, raw signal 60, differentiated signal 80 and trigger signal 90th
  • FIG. 1 shows a device for identifying plastic and / or optionally one or more of its additives 1.
  • the device 1 comprises a pulse light source 2, here in the form of a laser, with which a sample 3 of the plastic to be identified is irradiated.
  • the re-emitted light from the sample 3 is detected via a filter 4 and a lens 5 by means of a sensor 6.
  • the raw signal obtained by the sensor 6 is processed by means of a signal processing 7 and by means of a differentiator 8 also a differentiated signal is generated.
  • a trigger is likewise generated by means of a trigger generation 9, which then triggers a first timer integrator 12a and via a delay 10 a second timer integrator 12b.
  • the signal (see FIG. 2) is integrated at different non-overlapping time periods of equal duration on the falling edge of the processed signal.
  • the two values which are provided by the two integrators 12a and 12b are related to each other, here supplied by means of quotient formation and the number thus obtained to an evaluation 14.
  • the evaluation 14 may include, among other things, that in a memory of the device, a plurality of reference codes for various combinations of plastics and their additives has been deposited and based on a comparison between these ratios and the determined index by the measurement then the plastic and / or its additives are identified.
  • a plurality of reference codes for various combinations of plastics and their additives has been deposited and based on a comparison between these ratios and the determined index by the measurement then the plastic and / or its additives are identified.
  • For the storage of such values / characteristic numbers it is possible, for example, to carry out repeated measurements of the same plastic with the same additives and then to store these in the memory, for example with an average value and a corresponding deviation.
  • ambiguous identification such a result can be displayed to a user accordingly and the plastic, if the method is used in recycling, can be sorted out separately and then possibly fed to a further identification method.
  • the ultrafast analog-to-digital converter can digitize the measured values of the sensor 6 directly behind or behind
  • Fig. 3 shows in schematic form parts of a device according to an embodiment of the present invention.
  • a spectrometer with addition for measuring the fluorescence decay time is shown.
  • an optical grating 21, which diffracts the light bundled by the lens 5, is additionally arranged in the detection beam path, in particular between lens 5, sensor 6 and sensor system 22 in FIG. 1.
  • the sensor 6, which is provided for the re-emitted light for detecting the fluorescence decay time constant, is arranged in the 0th order of the light diffracted by the optical grating 21.
  • FIG. 4 shows fluorescence decay times at summed fluorescence decay time of polystyrene with and without various flame retardants.
  • FIG. 4 shows various fluorescence decay times on summated fluorescence with excitation at a wavelength of 266 nm of impact polystyrene, HIPS (high impact polystyrene) without flame retardants and with various flame retardants.
  • the wavelength of 266 nm can be generated, for example, with an NdYAG laser which has a fundamental wavelength of 1064 nm by frequency multiplication in a manner already known.
  • the fluorescence decay time is 10.2ns for HIPS without flame retardancy, whereas for the HIPS without flame retardation it is 10.2ns Flame retardant TBBPA and SD2O3 smaller by more than half, here namely 3.9ns.
  • Fig. 5 shows fluorescence decay time constants of various substances at summated fluorescence.
  • FIG. 5 shows the mono-exponential fluorescence decay times ⁇ at summed fluorescence for various materials, in particular plastics at an excitation wavelength of 266 nm.
  • the following abbreviations are used:
  • PC polycarbonate (ABS: acrylonitrile-butadiene-styrene)
  • FIG. 6 represents the bi-exponential decay times of various bulk materials. In principle, however, a mono-exponential decay time determination for certain plastics may already be sufficient:
  • Table 1 above shows the fluorescence decay constants t in ns of various technical polymers averaged over a measuring time of 10 s.
  • the fluorescence excitation took place at a wavelength of 403 nm, mono-exponential evaluation: ⁇ , bi-exponential evaluation: ti and ⁇ .
  • the usual light sources can be used for short flashes of light, such as gas discharge lamps (flash lamps), preferably with hydrogen-containing gas fillings, or semiconductor lasers that are versatile to the Available and can be operated easily.
  • the pulse duration can be in the range of nanoseconds, and the time course of the fluorescent light in response to the excitation pulse can be obtained in a known manner, for example by deconvolution. For this it is not necessary, but advantageous, if the duration of the excitation pulse is considerably smaller than the fluorescence lifetime; this can be achieved efficiently with semiconductor lasers.
  • the fluorescence lifetime spectra were recorded with a PicoQuant FluoTime 300.
  • the light source was a PicoQuant PicoHarp 300 controlled PC-405 laser with 0.4 mW power at a pulse frequency of 20 MHz and an excitation wavelength of 403 nm.
  • the detection wavelength was determined by taking a lifetime-dependent fluorescence spectrum.
  • the respective fluorescence intensities of the fluorescence components with predominantly short (tFiuoi) and predominantly long fluorescence lifetime (tFiuo2) were recorded at the corresponding spectral wavelengths.
  • the selected ranges result from the nature of each sample measured and are not necessarily representative of the individual, contained in the sample, fluorophores.
  • Detection was subsequently performed at the wavelength corresponding to the fluorescence maximum of the long fluorescence lifetime components (Table 2).
  • the measurement duration of the fluorescence lifetime determination was 1.0 ms or 10 s.
  • the resulting decay curves were evaluated with the software FluoFit from Picoquant. For this purpose, the maximum of the measurement curve was determined and its two abscissa sections considered.
  • the second abscissa section comprises a range of 40 ns (to tzns) starting at t yns which gives the fluorescence lifetime xi (Table 3).
  • Table 3 Selection of the time ranges as a function of the decay curve for bi-exponential fitting.
  • the excitation structure of the laser was not considered due to its low half-width.
  • the values obtained are therefore not absolute, but must be adapted to the device.
  • the deconvoluted data were evaluated bi-exponentially for better reproducibility. This can ensure a higher level of security during identification.
  • the fluorescence decay time constants of PET drinking bottles are determined, in particular PET water bottles or their shredder material, in order to be able to distinguish this from PET material, which can be mixed with oils and other lipophilic substances such as petrol fuel, diesel fuel and lubricating oils (engine oil) was contaminated. This contact may functionally or by misuse, eg unauthorized filling of fuels in drinking bottles, have arisen.
  • the following fluorescence decay times resulted:
  • Table 4 Fluorescence decay constants ⁇ , ⁇ , i2 in ns of PET materials with various impurities averaged over 10 s measurement duration. Fluorescence excitation at 403 nm, detection at 450 nm. Mono-exponential evaluation: ⁇ ; bi- exponential evaluation: ⁇ and X2.
  • the fluorescence decay times were again determined integrating over a period of 10 s and gave very good reproducible values even with different samples.
  • the measuring time could be shortened to 1 ms without problems and showed only insignificantly more scattering measured values.
  • the detection wavelength was determined here by taking a lifetime-dependent fluorescence spectrum from a PET derivative.
  • the selected ranges result from the nature of each sample measured and are not necessarily representative of the individual, contained in the sample, fluorophores. Detection was subsequently performed at the wavelength corresponding to the fluorescence maximum of the long fluorescence lifetime components (450 nm).
  • the measurement duration of the fluorescence lifetime determination was 1.0 ms or 10 s.
  • the resulting decay curves were evaluated with the software FluoFit from Picoquant.
  • the maximum of the measurement curve was determined and considered with respect to two abscissa sections.
  • the second abscissa section comprises, starting at an abscissa section 5 ns behind the maximum (tsns), a range of 40 ns (to sns), from which the fluorescence lifetime X 2 results.
  • the excitation structure of the laser was not considered due to its low half-width.
  • the values obtained are therefore not absolute, but must be adapted to the device.
  • the described method explains the reliable differentiation of the different samples and can be adapted to other experimental arrangements.
  • the cleaning was carried out first with manual wiping with cloth towels; with compact PET parts, crushing into flakes took place. Thereafter, the PET flakes were washed in a mixture of 3% aqueous NaOH solution (100 ml) and 15% aqueous sodium dodecyl sulfate solution (50 ml) with stirring for 2 h at 85 ° C. Finally, the test specimens were dried with tissue paper, air pressure and then at 60 ° C for 16 h.
  • the fluorescence decay curves of the polyethylenes contain high bi-exponential fractions, and in the case of bi-exponential analysis of the curves, 0.456 ns and 4.655 ns are found for 0.155 ns LDPE and 4.238 ns for HDPE and 0.217 ns and 4.923 ns for UHPE; see Table 5 below. Using the bi-exponential portions, the assignment of the polyethylenes is considerably simplified and considerably safer.
  • Table 5 Fluorescence decay constants ⁇ in ns of various PE materials averaged over 10 s measurement duration. Fluorescence excitation at 403 nm, detection at 450 nm. Mono-exponential evaluation: ⁇ , bi-exponential evaluation: ⁇ and T2. The standard deviation is given in brackets for a less favorable 1 ms integration time and 10 independent material samples.
  • the values ⁇ and X2 in Table 5 have been determined at 10 s integration time and are to be regarded as reliable means. To estimate the effect of measurement errors, the standard deviations for the less favorable 1 ms integration time were determined from the measurements of 10 independent samples. Even taking into account the now unfavorable boundary conditions, a clear identification of the polymer materials is possible.
  • the selected ranges result from the nature of each sample measured and are not necessarily representative of the individual, contained in the sample, fluorophores.
  • the detection was subsequently performed at the wavelength corresponding to the Fluorescence maximum of the components with long fluorescence lifetime corresponds to (500 nm).
  • the measurement duration of the fluorescence lifetime determination was once again 1.0 ms or 10 s.
  • the resulting decay curves were evaluated with the software FluoFit from Picoquant.
  • the maximum of the measurement curve was determined and considered with respect to two abscissa sections.
  • the second abscissa section comprises a range of 40 ns (to t43n S ), from which the fluorescence lifetime ⁇ 2 results.
  • the excitation structure of the laser was not taken into account again due to its short half-width.
  • the values obtained are not absolute The method described, however, explains the reliable differentiation of the different samples and can be adapted to other experimental arrangements.
  • the silicones can be unambiguously assigned via the two decay constants (.tau. And T2).
  • Two clusters are obtained by obtaining short decay constants ⁇ and longer ones for dehesive materials (Nos. 3 to 5) for the commercial silicone elastomer Tectosil® (Nos. 1 and 2).
  • the processing of Tectosil® has a smaller but characteristic influence (Nos. 1 and 2).
  • the decay constants ⁇ 2 are very long compared to other polymers and can be used for assignment to silicones and also for fine assignment.
  • This size also differentiates the preparation of the dehesive materials by finding a longer constant using a tin catalyst (# 3) and a shorter one for platinum catalysts (# 4 and # 5).
  • a commercially available silicone tube (No. 6) in its data corresponds more to the Dehesiv materials, but can be clearly distinguished from these; Materials from various manufacturers and for various uses can thus be efficiently distinguished and also classified. In Figure 5, this is shown in two dimensions.
  • the fluorescence decay times were determined here integrating over a period of 10 s and gave very good reproducible values, even with different samples.
  • the measuring time could be shortened to 1 ms without problems and showed only insignificantly more scattering measured values.
  • the fluorescence lifetime spectra were recorded with a PicoQuant FluoTime 300.
  • the light source was a PicoQuant PicoHarp 300 controlled PC-405 laser with 0.4 mW power at a pulse frequency of 20 MHz and an excitation wavelength of 403 nm.
  • the measurement duration of the fluorescence lifetime determination was 1.0 ms or 10 s.
  • the resulting decay curves were evaluated with the software FluoFit from Picoquant.
  • the maximum of the measurement curve was determined for Tectosil and considered with respect to two abscissa sections.
  • the second abscissa section comprises, starting at an abscissa section 2 ns behind the maximum (t2ns), a range of 40 ns (to U2ns), from which the fluorescence lifetime i 2 results.
  • the deconvoluted data were evaluated bi-exponentially for better reproducibility. As a result, a higher sorting security can be ensured.
  • the detection of polymers over the fluorescence decay constant can be used to sort the materials for recycling, for example, thermoplastics, where reuse can be easily accomplished.
  • plastics that are to be chemically treated such as when using used Thermodure, since it then manages to supply the processes with a uniform starting material, with which they can then be operated more stable.
  • recyclables such as platinum catalysts
  • the process can also be used outside of recycling to visually recognize plastics, such as in product control, especially in high-quality end products in which various starting materials are brought together.
  • the integration over a defined period of time expediently, the measurements are made before the first half-life and measurements after the first half-life, is of particular advantage because this significantly improves the signal-to-noise ratio (the fluorescence light of the sample is used more efficiently ).
  • the measurement processes can take place at intervals of one to two nanoseconds with integration times of likewise about one to two nanoseconds. Measurements with such a temporal resolution pose no problem electronically.
  • the measuring process can be further simplified if the plastic sample is optically excited not only once but periodically.
  • the measurement can advantageously be carried out within a fluorescence decay process by delaying the detection of the required integrated signals with periodic excitation and triggered by the excitation pulse;
  • a separation can be carried out, for example, with several parallel-operating phase-sensitive detectors (PSD), over which, over different time periods of the decay curve integrating, the intensities measured become. It is not necessary to determine the absolute cooldown.
  • PSD phase-sensitive detectors
  • Device-specific raw data can also be used here as long as they are sufficiently reproducible; In all the devices used here, excellent reproducibility of the measured values has also resulted as raw data (eg not corrected by deconvolution). The unproblematic use of raw data also simplifies the process even further.
  • PET materials can be clearly identified with respect to contamination by their previous use and sorted sorted by machine in this way; This is particularly important for distinguishing PET material contaminated with mineral oil products from uncontaminated material, including for use in the food industry.
  • silicone materials can be assigned and distinguished, as shown here with silicone elastomers and dehesive films.
  • a refined evaluation allows conclusions about the processing of the respective silicone.
  • the different catalysts for the production of silicone-dehesive material are reflected in particular in the T2 time constant, can be efficiently detected on the auxiliaries such as platinum catalysts and recovered sorted.
  • the method can also be used for routine product control, since it can be easily automated.
  • the PE materials LDPE, HDPE and UHDPE for example, can also be clearly identified and are on this Sort by type sortable.
  • substances and / or additives in or on materials can be easily and highly reliably differentiated by FLZA, ie in particular with the aid of the fluorescence decay time constant.
  • the measurement of the fluorescence lifetime - both in the case of a mono-exponential evaluation as well as in the case of a bi-, tri- or even higher exponential evaluation - is possible in a simple manner with simultaneous high reliability in their determination.
  • a further advantage is that an FLZA, in particular the measurement of the fluorescence lifetime, can be implemented simply and thus can be used in particular in the recycling of large quantities of plastics.
  • the FLZA and its evaluation require only a few nanoseconds, so that, for example, plastic flakes reliably, for example, on a För- derband be irradiated with the light and the re-emitted light can then be used for FLZA.
  • FIGS. 7 and 8 show intensity distributions as well as fluorescence lifetime measurements of polystyrene (FIG. 7) and high impact polystyrene HIPS (FIG. 8).
  • a two-dimensional intensity distribution (“continuous plot") is shown.
  • the lower left shows the corresponding one-dimensional intensity distribution along a line in the spectrum from left to right This results in a decay time constant of 7.7 ns for polystyrene (FIG. 7) and in FIG. 8 a decay time of 10.2 ns for high impact polystyrene.
  • the invention has, inter alia, the advantages that a particularly reliable identification of substances and / or their additives is made possible.
  • the invention offers the advantage that in particular plastics and especially in the field of recycling can be identified quickly and in large quantities in an extremely reliable manner and if appropriate can then be separated from a material flow in order to be further processed.
  • Another advantage is that substances, especially plastics or chemically similar substances can be reliably distinguished.

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Abstract

L'invention concerne un dispositif d'identification d'une ou de plusieurs substances dans un matériau, ce dernier se présentant notamment sous la forme de granulés, ledit dispositif comprenant au moins une source lumineuse (2), de préférence sous la forme d'un laser, servant à exposer un échantillon (3) du matériau à une lumière présentant au moins une longueur d'onde, un détecteur (6) servant à détecter la lumière renvoyée et/ou transmise par l'échantillon, et un dispositif d'analyse servant à l'analyse spectroscopique de la lumière détectée, ledit dispositif d'analyse coopérant avec le détecteur et étant conçu pour, au moyen • a) d'une spectroscopie UV/VIS et/ou • b) d'une spectroscopie de fluorescence et/ou • c) d'une spectroscopie Raman et/ou • d) d'une spectroscopie d'absorption, analyser la lumière détectée, et fournir un premier résultat d'identification pour au moins une substance de l'échantillon et, si le premier résultat d'identification est équivoque, fournir un deuxième résultat d'identification pour ladite au moins une substance, sur la base • e) d'une analyse de temps d'affaiblissement de la lumière fluorescente, ladite au moins une substance étant au moins partiellement identifiée ensuite sur la base du premier résultat d'identification ou sur la base du premier et du deuxième résultat d'identification.
EP17761795.8A 2016-08-04 2017-08-01 Dispositif d'identification de substances Pending EP3494383A1 (fr)

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PCT/DE2017/200077 WO2018024300A1 (fr) 2016-08-04 2017-08-01 Dispositif d'identification de substances

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Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102018222185A1 (de) * 2018-12-18 2020-06-18 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren und Vorrichtung zum Recycling von LED-Komponenten aus Altlampenmischungen sowie Verwendung der Vorrichtung
DE102019127708A1 (de) * 2019-10-15 2021-04-15 Kurtz Gmbh Verfahren und Vorrichtung zum Sortieren und/oder Abmessen der Menge von Schaumstoffpartikeln
DE102020201582A1 (de) * 2020-02-10 2021-08-12 Continental Reifen Deutschland Gmbh Fahrzeugluftreifen mit Geräuschabsorber und Verfahren zur Detektion eines Fahrzeugluftreifens mit Geräuschabsorber sowie zum Recycling eines Fahrzeugluftreifens mit Geräuschabsorber
DE102020201585A1 (de) * 2020-02-10 2021-08-12 Continental Reifen Deutschland Gmbh Fahrzeugluftreifen mit Geräuschabsorber und Verfahren zur Detektion eines Fahrzeugluftreifens mit Geräuschabsorber sowie zum Recycling eines Fahrzeugluftreifens mit Geräuschabsorber
DE102021119662A1 (de) * 2021-07-28 2023-02-02 Dpg Deutsche Pfandsystem Gmbh Gebinde aus rezyklierbarem Kunststoff sowie Verfahren und Vorrichtung zum Zurücknehmen eines solchen Gebindes

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4137008A1 (de) * 1991-11-11 1993-05-13 Heribert F Dr Ing Broicher Vorrichtung zur feststellung von qualitaetsaenderungen von massenguetern auf laufenden foerderbaendern
DE4210970C2 (de) * 1992-04-02 1996-10-17 Markus Dipl Chem Sauer Verfahren zur simultanen optischen qualitativen und quantitativen Erfassung von verschiedenen mit Fluorochromen oder Fluorogenen markierten Molekülen eines Gemisches mittels Laserspektroskopie
DE4213323A1 (de) * 1992-04-23 1993-10-28 Bayer Ag Verbessertes Verfahren zur Kennzeichnung von Kunststoffen
DE4312915A1 (de) 1993-04-10 1994-10-13 Laser Labor Adlershof Gmbh Verfahren und Anordnung zur IR-spektroskopischen Trennung von Kunststoffen
DE4340914A1 (de) * 1993-11-27 1995-06-08 Bruker Analytische Messtechnik Verfahren zur routinemäßigen Identifikation von Kunststoffen
DE4433937A1 (de) * 1994-09-23 1996-03-28 Martin Dipl Ing Huonker Verfahren zur Markierung und Erkennung von Kunststoffen
WO1998019800A1 (fr) 1996-11-04 1998-05-14 National Recovery Technologies, Inc. Application d'une spectroscopie raman permettant d'identifier et de trier des plastiques post-consommation de façon a les recycler
GB2330409A (en) * 1997-10-17 1999-04-21 Univ Cranfield Identifying plastics for recycling
DE19816881B4 (de) 1998-04-17 2012-01-05 Gunther Krieg Verfahren und Vorrichtung zur Detektion und Unterscheidung zwischen Kontaminationen und Gutstoffen sowie zwischen verschiedenen Farben in Feststoffpartikeln
US6412642B2 (en) * 1999-11-15 2002-07-02 Alcan International Limited Method of applying marking to metal sheet for scrap sorting purposes
DE10149505A1 (de) * 2001-10-02 2003-04-10 Krieg Gunther Verfahren und Vorrichtung zur Selektierung von Kunststoffen und anderen Materialien bezüglich Farbe und Zusammensetzung
US20050095715A1 (en) 2003-10-31 2005-05-05 General Electric Company Tagging Material for Polymers, Methods, and Articles Made Thereby
US7359040B1 (en) * 2006-10-13 2008-04-15 Itt Manufacturing Enterprises, Inc. Simultaneous capture of fluorescence signature and raman signature for spectroscopy analysis
TWI468653B (zh) * 2010-03-31 2015-01-11 Oto Photonics Inc 能接收零階光譜分量及一階光譜分量之微型光譜儀
DE102012005542A1 (de) * 2012-03-21 2013-09-26 Polysecure Gmbh Material mit Marker und Verfahren zum Sortieren einer Mischung von Materialien
DE102012012772A1 (de) 2012-06-22 2013-12-24 Ludwig-Maximilians-Universität München Markierung von Polymermaterialien mit Fluoreszenzfarbstoffen für deren eindeutige automatische Sortierung
DE102014004529A1 (de) * 2014-03-27 2015-10-15 Ludwig-Maximilians-Universität München Die automatische Sortierung von Polymermaterialien anhand der Fluoreszenzabklingzeit der Eigenfluoreszenz und der Fluoreszenz von Markierungsstoffen
DE102015001955A1 (de) * 2015-02-13 2016-09-01 Heinz Langhals Die automatische Erkennung von Kunststoffen anhand einer Gaußanalyse ihrer Autofluoreszenz für ihre maschinelle Sortierung für Recycling-Zwecke

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