DE102013011642A1 - Method for determining carbochemically relevant characteristics of lignite by means of fluorescence photometry - Google Patents

Abstract

The invention relates to a monochromatic, standard-related, optical measuring method for luminescence-photometric parameter determination in carbochemistry. It preferably serves to quantify hydrocarbon leading lignite ingredients and lignite thermal hydrocarbon products. The object of the invention is to provide a method for measuring luminescence photometric parameters of weakly luminescent substances, which optically enables the determination in particular of the tar yield or of the bitumen content of brown coal. The object is achieved in that a comparison of the measured at a defined wavelength luminescence dusty processed, homogenized sample and a luminescence blendenanordnungslos, monochromatically and when using low-magnification lens systems as an integral measurement of all fluorescent coal components, wherein an amplification is necessary to quantify the signal and according to the invention, the luminescence emissions of the sample material and of the luminescence standard in the region of the highest susceptibility of the photomultiplier / spectrometer are measured.

Description

The invention relates to a monochromatic, standard-related, optical measuring method for luminescence-photometric parameter determination in carbochemistry. It preferably serves to quantify hydrocarbon leading lignite ingredients and lignite thermal hydrocarbon products.

Relative spectral and monochromatic measuring methods are known for the luminescence-photometric parameter determination of luminescent substances in sediments, soils, rotting products, petroleum boulders and lignites [1-8]. These are based in the monochromatic range on the comparison of a particle emission shielded from the sample environment with suitable luminescence standards (reference). The latter are technical glasses of high long-term stability in the emission (fading-free), the emission intensity is reduced by partial masking and thus equal in size to the measured carbon particles. The spectral measurement of the emission is also carried out on isolated particles in the microscopic range. In this case, the luminescent microcomponents to be measured are shielded from the environment by defined diaphragm arrangements, or the environmental influence is compensated by means of mathematical algorithms (background compensation).

These methods are not suitable for the parameter determination of luminescent substances by means of integral measurement in the described sense of the method, since it is always a punctiform, performed in the micrometer range registration of the emission intensity, in order to avoid fluorescence influences the environment messfeldeengende aperture arrangements are used, the integral Measurement according to the invention would further reduce the already low luminescence intensity of the sample. DD 208 416 B1 is concerned with a similar problem, but using a non-standard and non-monochromatic, ie characterized by the spectral susceptibility of the individual components of the optical system clearly differing from the present invention.

The state-of-the-art in the exploration of contaminated sites is the Rapid Optical Screening Tool (ROSTTM) for the investigation of hydrocarbon contaminations in sediments and soils via the registry of the emission generated by pulsed laser-induced fluorescence [9]. A reference-dependent quantification of the signal in relation to the amount of contaminants is not the subject of the technology. An application of ROST ™ in the sense of the use claims of the invention described here is not relevant.

For the determination of the tar yield or the bitumen content of lignite, there are no reference-related methods on a luminescence photometric basis.

The object of the invention is to provide a method for measuring luminescence photometric parameters of weakly luminescent substances, which optically enables the determination in particular of the tar yield or of the bitumen content of brown coal.

The object is achieved in that a comparison of the measured at a defined wavelength luminescence dusty processed, homogenized sample and a luminescence blendenanordnungslos, monochromatically and when using low-magnification lens systems as an integral measurement of all fluorescent coal components, wherein an amplification is necessary to quantify the signal and according to the invention, the luminescence emissions of the sample material and of the luminescence standard in the region of the highest susceptibility of the photomultiplier / spectrometer are measured.

This makes a direct comparison of the luminescence emissions of sample material and standard possible. It is irrelevant whether the luminescence standard in its emission is of the same order of magnitude as the measured sample, or whether its intensity exceeds the luminescence emission of the sample by a multiple.

The method makes it possible to determine the corresponding parameters on very weakly luminescent substances such as lignite. The method also has the advantage that the determination of tar yield or bitumen content of brown coal in a very short time, without drying and chemical analysis can be made flöz- or Lagersstätten- (areal) specific.

The invention will be clarified by the following embodiment:
For clarification is in the structure of a luminescence-photometric measuring arrangement shown. The measuring arrangement preferably used to ensure the process-specific measurable luminescence effect consists of a reflected-light luminescence microscope 1 known construction, or a comparable optical arrangement, equipped with a luminescence excitation serving, mainly in the ultraviolet and short-wave blue range permeable filter assembly 2 and a dichromatic splitter mirror 3 . and a barrier filter combination for eliminating stray short-wave excitation radiation (UV / blue) 4 , The beam path must be designed to ensure sufficient excitation energy and for the inventive integral measurement of larger sample areas free of any diaphragm arrangement.

In a first step, the system is calibrated analogously to the algorithm described below for the sample measurement.

The powdered brown coal dust preparation (particle size 0-0.2 mm) 5 Outgoing substance-specific luminescence emission is achieved by means of small magnification lens systems 6 excited by UV / short-wave blue light (integral large-field measurement), the emission detected in the same way and a defined, very limited wavelength range monochromatic in the photomultiplier / spectrometer (SPECTRO / SEV) 7 , the evaluation units 8th known type downstream, registered. The photocurrent measurable in the multiplier / spectrometer is thus a measure of the luminescence emission of sample material and standard that can be registered as a function of the susceptibility of the measuring device.

Since the luminescence intensity of lignite and carbochemically relevant parameters, such as the Schwelteerausbeute, the bitumen content or the gain of liquid product in the hydrogenation natural close relations exist, obtained in the manner described relative surface luminescence emission intensities of the largely homogenized lignite samples with the known manner by chemical analysis certain carbochemical parameters in calibration charts compiled. With sufficient densification of the pairs of values, the determination of carbochemically relevant lignite parameters is possible in a simple and fast way by means of luminescence photometric measurement, without further elaborate chemical analysis, of fl ooring and storage site (areal) specificity.

Literature:

• [1] Jacob, H .: "Microscopic photometry of organic matter from soils. II. Fluorescence photometry of forest and agricultural rotting products. "- Bodenkultur, 24, pp. 1-40, Vienna 1973 ;
• [2] Jacob, H .: "Fluorescence Microscopy and Photometry of the Organic Substance of Sediments and Soils." - In: Freund, H .: Handbuch der Mikroskopie in der Technik. 4, 2, pp. 369-391, Umschau Verlag Frankfurt a. M. 1973 ;
• [3] Ottenjann, K., Teichmüller, M. & M. Wolf: "Spectral fluorescence measurements on sporinites with incident-light excitation, a microscopic method for determining the degree of coalification of low-carbon coals." - Progress. Geol. Rheinld. u. Westf. 24, pp. 1-36, Krefeld 1974 ;
• [4] Ottenjann, K., Teichmüller, M. & M. Wolf: "Spectral fluorescence of sporinites in reflected light and their applicability for coalification studies." - In: Alpern, B. (Hsg.): Pétrographie organique et potentiel pétrolier, S. 49-65, published by CNRS Paris 1975 ;
• [5] Jacob, H .: "The Application of Microphotometry in Organic Petrology." - Leitz Communications for Science and Technology 7, 7, pp. 209-216, Wetzlar 1980 ;
• [6] Ottenjann, K .: Spectral Fluorescence Microphotometry of Coals and Oil Shales. "- Leitz Communications for Science and Technology 7, 7, pp. 262-273, Wetzlar 1980 ;
• [7] Ottenjann, K .: Improvements in Microscopic Photometric Fluorescence Measurement on Carbon Macerals. "- Zeiss Information, 26, 93, pp. 40-46, Oberkochen 1982 ; International Commission for Coalpetrology [ICCP]: "International Lexicon for Coalpetrology." - 1st & 2nd edition with additions, publisher CRNS Paris 1963, 1965, 1973, 1975 ;
• [8th] Martinez, L., Pradier, B. & Ph. Bertrand: "La microspectrofluorimétrie en pétrologie organique. Methodology et application à l'étude de la maturation des algues fossils du Toarcien du basin de Paris. "- CR Acad. Sc., T. 304, 111/9, p. 441-446, Paris 1987) ;
• [9] Neuhaus, M. & N. Ehle: "Exploration of Hydrocarbon Contaminations by means of Pressure Soundings." - WLB Water, Air and Soil, 10, pp. 69-71, Stuttgart 2000) ;

LIST OF REFERENCE NUMBERS

1

Epi-luminescence

2

A filter assembly

3

dichromatic splitter mirror

4

Blocking filter combination

5

Powdered lignite dust preparation (particle size 0-0.2 mm)

6

low magnification lens systems

7

Photomultiplier / spectrometer (SPECTRO / SEV)

8th

Processors

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DD 208416 B1 [0003]

Claims (1)

Process for the photometric determination of carbochemically important components in brown coal, such as bitumen content, smoldering yield or the amount of lignite-based liquid hydrocarbons, characterized by the following features: a) The luminescence of the powdery sample material is determined by monochromatic means of photomultiplier tube (SEV) or spectrometer. b) The measurement integrally registers the entire image field using a low magnification optical system. c) The results are related to a defined fluorescence standard with monochromatic emission characteristics.

Images