WO2002008738A1 - Appareil pour analyse diffractométrique en ligne - Google Patents

Appareil pour analyse diffractométrique en ligne Download PDF

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Publication number
WO2002008738A1
WO2002008738A1 PCT/AU2001/000901 AU0100901W WO0208738A1 WO 2002008738 A1 WO2002008738 A1 WO 2002008738A1 AU 0100901 W AU0100901 W AU 0100901W WO 0208738 A1 WO0208738 A1 WO 0208738A1
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WO
WIPO (PCT)
Prior art keywords
sample
distribution chamber
sample flow
ray diffraction
stream
Prior art date
Application number
PCT/AU2001/000901
Other languages
English (en)
Inventor
Ian Charles Madsen
Jonian Ivanov Nikolov
Original Assignee
Commonwealth Scientific And Industrial Research Organisation
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 Commonwealth Scientific And Industrial Research Organisation filed Critical Commonwealth Scientific And Industrial Research Organisation
Priority to AU2001276157A priority Critical patent/AU2001276157A1/en
Publication of WO2002008738A1 publication Critical patent/WO2002008738A1/fr

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
    • G01N23/207—Diffractometry using detectors, e.g. using a probe in a central position and one or more displaceable detectors in circumferential positions

Definitions

  • This invention relates to an apparatus for performing X-ray diffraction analysis and in particular relates to performing X-ray diffraction of solid/liquid mixtures in a processing line environment.
  • the invention also relates to a method for analysing solid/liquid mixtures using x-ray diffraction analysis.
  • Powder X-ray diffraction analysis has mainly been confined to material investigations conducted on materials away from a processing or on-line environment. However, as in most specialised fields, traditional applications are being extended to new methods of analysis. Just as X-ray diffraction has advanced to enable measurement of materials properties such as orientation and grain stress, to improve the usefulness of this analysis technique the use of X- ray diffraction as an analysis technique for on-line processing streams would be highly advantageous in the control of the material properties of the stream. This is particularly the case in the mineral processing industry. As an on-line analysis it is desirable for the concentration of the slurry to be the same as in the process. For mineral processing this may be approximately 40% v/v.
  • US 4,090,073 discloses a method of using X-ray diffraction to determine the mineral composition in an aqueous mineral slurry.
  • this method is not as effective as desired, since it relies on the collection of a limited range of the X-ray pattern.
  • High energy (short wavelength) X-rays are required for the transmission mode required in this prior art invention. These high energy X-rays produce a compressed pattern and discrimination between peaks can be difficult.
  • the invention provides an apparatus for on-line analysing a stream of solid/liquid mixture including a means for removing a sample flow from the stream of solid/liquid mixture, a means for preparing and presenting the sample flow with a substantially flat upper surface to a measurement station for X-ray diffraction measurement, a measurement station including an X-ray generator and position sensitive detector for detecting X-ray diffraction patterns from the prepared sample flow, and processor means for analysing the X-ray diffraction patterns to determine the composition of substances in the sample from each diffraction pattern and for providing a series of sequential composition determinations thereby representing the composition of the substances in the sample flow
  • the position sensitive detector for detecting the X-ray diffraction patterns of the sample is a curved position sensitive detector or area detector capable of simultaneous collection of a wide angle range of the X-ray diffractogram.
  • an apparatus for presenting a sample from a solid/liquid material flow for X-ray diffraction measurements having an inflow conduit with an inlet for receiving the sample flow from the material flow, the conduit communicating with a distribution chamber, the distribution chamber communicating with an analysis region and an apparatus discharge, whereby the sample flow passes through the distribution chamber to the analysis region before passing to the apparatus discharge, and wherein the distribution chamber is adapted to provide a substantially flat upper surface of the sample flow in the analysis region.
  • the distribution chamber preferably diverges outwardly from the conduit and is provided with a plurality of outlets to the analysis region.
  • the apparatus preferably further includes a motion generation means for imparting centrifugal motion to the solid/liquid sample flow in the distribution chamber.
  • the motion generation means preferably rotates the distribution chamber about an axis.
  • the rotational axis of the distribution chamber preferably extends through the in flow conduit and may be co-axial.
  • the X-ray diffraction is conducted in reflection mode.
  • the substantially flat upper surface of the sample flow has no window or other barrier between this surface and the X-ray radiation source.
  • Preferably wide angle data collection is used to detect the reflected/refracted radiation.
  • a method for continuously presenting a sample from a stream of solid/liquid mixture containing crystalline substances including the steps of: extracting a sample flow from the stream; - feeding the sample flow continuously upwardly into a distribution chamber, imparting a centrifugal motion to the sample flow as it passes upwardly through the distribution chamber to an analysis region in the distribution chamber thereby presenting a substantially flat upper surface of the sample flow to an X-ray radiation source for performing X-ray diffraction measurements, and continuously discharging the sample from the distribution chamber.
  • centrifugal motion imparted to the sample counteracts surface tension forces in the upper surface of the solid/liquid sample, presenting a flat surface over the analysing region through which the X-ray diffraction measurements are performed.
  • a method of analysing a stream of solid/liquid mixture including:
  • the continuous withdrawal of a sample from the process stream allows its analysis on a continuous basis and thus the provision of substantially real time or current production data on which decisions can be made to control the process.
  • control may be effected automatically, for example as in a closed loop feedback system, or manually by a process operator.
  • X-ray diffraction analysis of solids in a solid/liquid mixture is only able to analyse the crystals of the material largely at the surface of the solid samples presented to the X-ray diffraction instrumentation.
  • the focus of the X-ray beam on the sample is tight, for example an area of the order of 10-30 mm 2 (typically 10 mm long x 1-3 mm wide) the more sample that is presented for analysis, the higher the confidence that the result is representative of the material in the process stream. It is also important for accuracy that the sample surface be very smooth and substantially flat.
  • slurry is used in its art recognised sense and means solid material mixed with a liquid. Embraced within this definition are sludges.
  • FIG. 1 is a diagrammatic representation of the main components of an apparatus embodying the invention
  • Figure 2(a) is a plan view of the distribution chamber in Figure 1
  • Figure 2(b) is an exploded side view of region A in Figure 2(a)
  • Figures 3(a) and 3(b) are XRD patterns using a mylar window and pure water respectively
  • Figures 4(a) and 4(b) show graphs of the XRD pattern for control solid/liquid sample with 50% v/v and 25% v/v solids respectively
  • Figures 5(a) and 5(b) are XRD patterns for control solid/liquid samples with 18% v/v and 5% v/v solids respectively
  • Figure 6 is a schematic view of an apparatus according to the present invention with X-ray source and detector.
  • the apparatus illustrated has a stage 1 including an upwardly flowing conduit 2 communicating with a distribution chamber 3.
  • the distribution chamber 3 is preferably mounted for rotational movement by a drive means (not shown). Alternatively the whole stage may be rotated to provide the desired centrifugal action.
  • the upper surface of the distribution chamber is provided with a plurality of outlets 5 to an analysis region 4.
  • Figure 2(a) shows outlets 5 located in the upper surface 9 and Figure 2(b) shows an enlarged sectional view of an outlet 5.
  • the size and location of these holes or outlets are selected so as to provide a substantially flat upper surface of the sample flow in the analysis region.
  • substantially flat we mean that interference from an irregular surface is reduced to a sufficient extent that meaningful data may be obtained in an analysis.
  • the stage 1 may be any shape but a frusto conical or cylindrical shape is preferred.
  • a sample discharge which may be an annular sleeve 6 provided to receive sample flow from the analysing region.
  • a solid/liquid mixture sample enters the distribution chamber 3 of the stage 1.
  • the sample may be withdrawn from the slurry stream by use of a pump.
  • the rotational motion of the chamber imparts a centrifugal motion to the sample as it progresses through the chamber.
  • Liquid effective seals are provided at appropriate places such as between the distribution chamber 3 and the conduit and rotational shaft drive for the distribution chamber and the conduits. This centrifugal motion is believed to counteract the surface tension forces on the surface of the sample providing a flat surface over the analysing region.
  • the centrifugal motion further has the benefit of progressing the analysed sample towards the discharge in distribution for X-ray measurements of the next sample.
  • the outlets 5 from the distribution chamber 3 may also have a lateral discharge component thereby imparting a lateral motion to the slurry as it exits the distribution chamber 3.
  • the centrifugal or swirling motion can be imparted to the sample without rotation of the distribution chamber 3 or stage 1.
  • the pumping rate of the sample from the slurry stream may also be used to influence the attainment of the desired substantially flat upper surface of the sample flow in the analysis region.
  • the outlets 5 may also be progressively larger towards the outer edges of the upper surface 9 of the distribution chamber 3. There may also be some advantage to slurry suspension by providing outlets upwardly oriented in the side of the chamber 3.
  • the measurement station 10 includes an X-ray source 11, and a position sensitive detector in the form of an area detector, 12 (120°), to detect diffracted radiation in the reflection mode.
  • a suitable processor means receives signals from detector 12 and presents the measurements in a desirable format.
  • Use of an area detector is preferred, although use of other types of detector such as single point detectors combined with a goniometer to sequentially measure the XRD pattern is also possible.
  • the area detector may collect the diffractogram over an angular range of 120° 2 ⁇ , typically spanning, 1° - 121° 2 ⁇ , but other ranges may be selected.
  • the X- ray diffraction instrumentation of the diffractomoter includes other components such as a tube stand and X-ray collecting devices.
  • the XRD instrumentation consists of the following - (i) INEL 3kw X-ray generator with RS232 interface to power the XRD tube.
  • the apparatus of the invention is preferably located (and consequently the method performed) in an air conditioned room to avoid instrument distortion due to temperature changes and to ensure protection of the electronic equipment.
  • a representative sample of a product stream can be conveyed into such a room located in proximity to the product stream.
  • the invention is suitable for any slurry process stream that can be transported from the processing line to the instrument. Examples of X-ray spectra are illustrated in Figures 3 - 5, with Figures 3(a) and (b) showing reference spectra using Mylar window (3a) and water (3b).
  • the slurry used in these experiments was a sample of concentrate from a lead-zinc smelter. It is desirable in commercial applications that the data quality is reasonably consistent over typically 25% - 50% by volume.
  • Figures 4(a) and 4b) demonstrate this consistency at 25% and 50% volume solids when run for 600 seconds.
  • Figures 5(a) and 5(b) illustrate the substantially poorer data when the sample had 18% and 5% by volume concentration. The poorer results at these lower volume concentrations is attributed to the influence of the water.
  • the spectrum for water is shown in Figure (3b). Although able to be used for slurries at these lower volume concentrations the apparatus provides better data at higher volume concentrations.
  • Peaks attributed to the Mylar window are those with an intensity of about 500 counts at 26 degrees and some of the "lumping" between about 10 and 40 degrees. These peaks are in areas that are of relevance for mineral slurries, as can be seen in Figures 4(a) and 4(b). It can be seen that this would interfere with data from the slurry sample.
  • the absence of a window also overcomes potential wear and scratching of window from abrasive slurries. This design also allows small incidence angles and reliable monitoring of phases with "large unit cell parameters"

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Analysing Materials By The Use Of Radiation (AREA)

Abstract

Cette invention a trait à un appareil (1) permettant de procéder à une analyse diffractométrique en ligne d'une veine de substances en suspension épaisse aqueuse constituée d'un mélange solides/liquide. Cet appareil (1) comprend un conduit d'amenée (2) recevant un échantillon de la veine de substances en suspension épaisse. Ce conduit est relié à une chambre de distribution (3) faisant pénétrer l'échantillon dans une zone d'analyse (4) où l'on effectue des mesures par diffraction des rayons X en faisant appel à des techniques de réflectance à partir d'une source de rayonnement (11) et en se servant d'un détecteur grand angle (12). L'échantillon est ensuite renvoyé dans la veine de suspension aqueuse. La chambre de distribution (3) imprime un mouvement centrifuge à l'échantillon de suspension, lequel échantillon prend alors la forme d'une surface plate au-dessus de la zone d'analyse (4).
PCT/AU2001/000901 2000-07-24 2001-07-24 Appareil pour analyse diffractométrique en ligne WO2002008738A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001276157A AU2001276157A1 (en) 2000-07-24 2001-07-24 On-line x-ray diffraction analyser

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPQ8937 2000-07-24
AUPQ8937A AUPQ893700A0 (en) 2000-07-24 2000-07-24 On-line x-ray diffraction analyser

Publications (1)

Publication Number Publication Date
WO2002008738A1 true WO2002008738A1 (fr) 2002-01-31

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PCT/AU2001/000901 WO2002008738A1 (fr) 2000-07-24 2001-07-24 Appareil pour analyse diffractométrique en ligne

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AU (1) AUPQ893700A0 (fr)
WO (1) WO2002008738A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112313505A (zh) * 2018-04-20 2021-02-02 奥图泰(芬兰)公司 X射线荧光分析仪和用于执行x射线荧光分析的方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5107527A (en) * 1986-06-02 1992-04-21 Outokumpu Oy Method and apparatus for analyzing sludgy materials
US5459770A (en) * 1991-10-17 1995-10-17 Cambridge Surface Analytics Ltd. X-ray diffractometer
US5712891A (en) * 1995-11-15 1998-01-27 Compagnie Generale Des Matieres Nucleaires Apparatus for the analysis of a solution by X-ray fluorescence
US5784432A (en) * 1996-01-24 1998-07-21 The Penn State Research Foundation Large angle solid state position sensitive x-ray detector system
US5923720A (en) * 1997-06-17 1999-07-13 Molecular Metrology, Inc. Angle dispersive x-ray spectrometer
US5982847A (en) * 1996-10-28 1999-11-09 Utah State University Compact X-ray fluorescence spectrometer for real-time wear metal analysis of lubrucating oils

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5107527A (en) * 1986-06-02 1992-04-21 Outokumpu Oy Method and apparatus for analyzing sludgy materials
US5459770A (en) * 1991-10-17 1995-10-17 Cambridge Surface Analytics Ltd. X-ray diffractometer
US5712891A (en) * 1995-11-15 1998-01-27 Compagnie Generale Des Matieres Nucleaires Apparatus for the analysis of a solution by X-ray fluorescence
US5784432A (en) * 1996-01-24 1998-07-21 The Penn State Research Foundation Large angle solid state position sensitive x-ray detector system
US5982847A (en) * 1996-10-28 1999-11-09 Utah State University Compact X-ray fluorescence spectrometer for real-time wear metal analysis of lubrucating oils
US5923720A (en) * 1997-06-17 1999-07-13 Molecular Metrology, Inc. Angle dispersive x-ray spectrometer

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112313505A (zh) * 2018-04-20 2021-02-02 奥图泰(芬兰)公司 X射线荧光分析仪和用于执行x射线荧光分析的方法

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Publication number Publication date
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