AU676846B2 - A method and apparatus for determining the particle size distribution, the solids content and the solute concentrations of a suspension of solids in a solution bearing a solute - Google Patents

Description

OPI DATE 15/03/94 AOJP DATE 09/06/94 APPN. 10 4U6920/93 PCT NUMBER PCT/AU93/00419 II11111111111 11111111111 III IIII IIIII AU9346920

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(51) International Patent Classifcation 5 International Publication Number: WO 94/04907 COIN 15/02, 15/06, 23/02 Al GOIN 29/00 (43) International Publication Date: 3 March 199 (03.03.94) (21) International Application Number: PCT AU9300419 (81) Designated States: AU, CA, RU, UA, US, European patent (AT, BE, CH, DE, DK, ES, FR, GB, GR, IE, IT, (22) International Filing Date: 16 August 1993 (16.08.93) LU, MC, NL, PT, SE).

Priority data: Published PL 4150 17 August 1992(17.08.92) AU With international search report.

(71) Applicant (for all designated States except USi: COMMON- WEALTH SCIENTIFIC AND INDUSTRIAL RE- SEARCH ORGANISATION [AU/AU]; Limestone Avenue, Campbell, ACT 2601 (AU).

(72) Inventor; and Inventor/Applicant (for US onlhi: SOWERB1', Brian, David IAU/AU]; 5 Bellbird Place, Kareela, NSW 2232 (AU).

(74) Agent: SHELSTON WATERS; 55 Clarence Street, Syd- 6 ney, NSW 2000 (AU).

(54) Title: A METHOD AND APPARATUS FOR DETERMINING THE PARTICLE SIZE DIP* JUTION, THE SOLIDS CONTENT AND THE SOLUTE CONCENTRATION OF A SUSPENSION OF SOLIDS IN A SOLUTION BEARING A SOLUTE (57) Abstract A measurement system (45) includes a tank (46) having an inlet and outlet (47, 48) through which a sample (49) flows prior and subsequent to measurement. A stirrer (50) disposed near the base of tank (46) 5 maintains a well mixed solution within the tank. Two immersion probes (52, 53) extend downwardly into the tank and include respective support tubes (54, 55) and sensor portions (56, 57). The sensor portions include respective gamma-ray transmission gauges and four pairs of ultrasonic transducers operating at different frequencies. Accordingly, probes (52, 53) allow themeasurement of attenuation and velocity of high and low frequency ultrasound through the sample as wellas measurement of attenuation of electromagnetic radiation through the sample. These measurements are utilised to derive an estimate of the solute concentration, 7 particle size distribution, concentration of solids and suspension and the solute concentration of the sample.

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WO 94/04907 PCr/AU93/00419 Title: A METHOD AND APPARATUS FOR DETERMINING THE PARTICLE SIZE DISTRIBUTION, THE SOLIDS CONTENT AND THE SOLUTE CONCENTRATION OF A SUSPENSION OF SOLIDS IN A SOLUTION BEARING A SOLUTE TECHNICAL FIELD This invention relates to a method and apparatus for determining the particle size distribution, the solids content and the solute concentration of a suspension of solids in a solution bearing a solute.

Advantageously, the invention is applicable for use in industrial processes such as in the precipitation section of the Bayer process.

BACKGROUND ART In certain industrial processes, such as the precipitation section of the Bayer process, it is desirable to monitor the particle size distribution of WO 94/04907 I'Cf/U93/0419 2 -2solids in a slurry or suspension under dynamic conditions and to determine the deviation of the actual particle size distribution from that desired. The invention will be herein described with particular reference to the Bayer process but is not limited to that use.

In the precipitation section of the Bayer process alumina is extracted and purified from bauxite. Bauxite is crushed and ground, then digested at elevated temperature (104-230°C) and pressure in a strong solution of caustic soda (80-110g Na20/litre). The residue, known as red mud, is separated from the solution by countercurrent decantation and filtration.

After cooling, the solution is supersaturated with respect to alumina. In the precipitation (crystallization) process the supersaturated solution is seeded with recycled alumina trihydrate fines and agitated in large tanks. The productivity of the Bayer process is limited by the slowest step, the precipitation of the alumina trihydrate from the liquor. After precipitation, the alumina is calcined at temperatures up to 1300 0 C and sold typically for commercial smelting to aluminium.

The goal of the precipitation section is to maximise alumina yield whilst maintaining product quality (particle size and strength) and seed balance.

Control variables in precipitation are temperature,

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WO 94/04907 I'Cr/A93/00419 3 starting alumina/caustic ratio, seed charge, caustic concentration, holding time and impurity levels (particularly organics).

It is desirable to minimise the proportion of fines (minus about 45 microns as well as minus about microns) in product alumina. These fines cause dust problems during handling operations and they cause significant flow and segregation problems in aluminium smelters. Fines are generated in the precipitation, calcining and handling stages of the plant. Improved control of the precipitation stage should produce less fines in precipitator product and a stronger alumina (Sang, "Factors affecting the attrition strength of alumina products", Light Metals, 1987, 121-127) which will in turn generate less fines in downstream calcining and handling.

The optimisation of alumina precipitation would benefit from the development of suitable on-line particle size analysers to monitor the proportions of both coarse and fine alumina at a number of cut-off points, for example at 20,45,75 and 100 microns.

Measurements preferably need to be made under the following plant conditions: caustic concentration 150 to 250g NaOH/litre; temperature 60 to 80°C; solids content up to 35wt%; scale build-up rates of about and variable air bubble concentration and size distribution.

WO 94/04907 1")C/AU93/00419 4 At present there are no commercially available on-line particle size monitors capable of this measurement.

The conventional method of measuring particle size distribution is to remove samples from the streams of interest and to perform screen analyses on these samples. A screen analysis involves a series of procedures by which a measurement is made of the proportion of the sample that remains on each of several screens having progressively smaller openings of known size. While this kind of measurement can provide a reasonably accurate determination of particle size distribution above about 45 microns, it is representative only of the particular sample taken, and cannot accurately and reliably indicate either the average condition in the flowstream over a period of time, or the changes that occur between sampling. Also the method is not applicable to fine fractions below microns, and is labour intensive and time consuming and therefore does not lend itself to either manual or automatic control.

There are three commercially available on-line particle size analysers which are finding significant use in the control of grinding circuits in the metalliferous mineral industry. However, these analysers are not suitable for use in alumina precipitation circuits, primarily because of air WO 94/04907 P'CT/AU93/00419 5 bubbles, scaling, caustic and high temperatures. These three on-line particle size analysers are based on ultrasonic attenuation (Autometrics PSM-400), a scanning laser microscope (Lasentec Par-Tec 200/300) and a reciprocating caliper (Outokumpu PSI-200). Alternative systems based on laser diffractions operate only on highly dilute solutions 5g solids/litre) and are not suitable for on-line use.

The on-stream laser scanning microscope (the Lasentec Par-Tec 200/300) does not require dilution of the process stream Hokanson, "In-line particle size measurement for improved process control in the mineral processing industry", Light Metals 1991, 39-42). In this analyser, the sample is scanned at constant speed by a high intensity laser beam and the reflected light is measured. Particles outside the focus of the laser beam are discriminated against on the basis of the rise time of the reflected light pulse. The main disadvantages of this technique are: it measures a very small sample and so flow conditions at the window affect the results; (ii) it does not operate in the presence of scale; (iii) it requires a transparent fluid; and (iv) the sensitivity to surface characteristics (shape and reflectivity) and air bubbles, while also being inaccurate on fine particles.

The reciprocating caliper device (Outokumpu PSI-200) WO 94/049)07 I'IIT/A U93/0041 9 6 uses a simple and direct measurement technique to determine the largest particle in the caliper. The device will not operate in the presence of scale and it cannot measure the fine particle size fractions.

The ultrasonic device (Autometrics PSM-400) determines the fraction of particles of size above a particular cut point (usually about 75 microns) by measuring ultrasonic attenuation at two frequencies.

One frequency is chosen where attenuation is not greatly affected by particle size and the second frequency is chosen to be sensitive to particle size. Combining these results allows one to derive a single point on the size distribution curve, provided that the shape of the size distribution curve remains fairly constant.

Measurements can be made on water-based slurries containing up to 30wt%. solids although air bubbles need to be eliminated before measurement.

The Autometrics PSM system, however, is not suitable for use in alumina precipitation plants as it is unable to correct for changes in caustic concentration, it is unable to determine the concentration of fine (minus 20 micron) particles and there is no correction for the effect of scaling or temperature.

The theory for ultrasonic theory attenuation methods shows that viscous and scattering losses provide the two main regions where direct calculation of size WO 94/04907 ll'Cr/AU9300419 7 from the observed attenuation is possible. If a pulsed beam of ultrasonic waves is transmitted through a sample slurry stream, the intensity of the transmitted beam is given approximately by: A Aoexp(-2ax) (1) where 2c absorption coefficient A initial intensity of wave 0 x distance travelled by wave The absorption coefficient is determined by two primary mechanisms, viscous and scattering losses.

Viscous losses are associated with the relative movement of liquid and solid. The particles vibrate in response to the ultrasonic wave but with a phase lag and different amplitude. Extremely small particles tend to move in phase with the fluid and losses are very small.

As size increases the particles tend to lag more and more behind the movement of the fluid and the loss per particle increases, but at the same time the solid-liquid interface area and therefore the loss per unit mass decrease. These opposing factors result in a viscous absorption maximum below about 3 microns particle size for frequencies above 800kHz, as shown in Figure 1 in which the calculated dependence of the absorption coefficient on particle size at different frequencies is plotted for suspensions in water (Riebel, U. and Loffler, U.S. Patent No. 4,706,509 November W-O 94/04907 PCr/AU93/00419 8 17, 1987). The ratio of particle density to fluid density and the fluid velocity are also important in determining viscous loss.

The second loss mechanism is the scattering of energy due to the absorption of a small amount of energy from the directed beam by each particle, and its subsequent radiation away from the point of absorption.

For ultrasonic wavelengths much greater than particle radius, it is possible to express the relationship between a and the properties of the solids and liquid by the equation: 2a c k r k(y-1) 2 s (2) S6 s 2 +(y+d)2 where r particle radius X wavelength of ultrasonic wave, c volume concentration of solids, k angular wavenumber of ultrasonic wave in water, y ratio of densities of particles and water, w angular frequency of ultrasonic wave, 4(3r r where 13 2v v kinematic viscosity of water, d 1 9 2d=l 2 43r WO 94/04907 PCrAU93-00419 9 This equation is valid up to about 20% solids, above which the dependence on c becomes more complex.

The first term in equation represents the attenuation due to scattering loss and the second due to viscous loss. For a given frequency, at very small particle sizes the viscous loss is predominant but as the size increases it becomes insignificant and the scattering loss becomes important.

For the case where X<<2rr (generally for particles well above 100m diameter and for frequencies of 1-10MHz), diffraction losses become important and equation must be replaced by the expression 2c 3c (3) 2r Relevant patents covering ultrasonic attenuation methods of particle size determination are U.S.

3,799,070 (Cushman et al), U.S. 4,706,509 (Riebel and Loffler) and U.S. 5,121,629 (Alba). U.S. 3,799,070 describes the method used in the Artometrics PSM-400 analysers in which only two measurements are made, namely ultrasonic attenuation at two frequencies. The signals resulting are processed electronically to provide information on particle size and percent solids by volume in the slurry. U.S. 4,706,509 (Riebel and Loffler) effectively extends the Cushman et al patent by measuring the ultrasonic attenuation at a plurality of WO 94/04907 PCr~/AU93/00419 10 frequencies and so is able to derive a wider range of particle size data. U.S. 5,121,629 (Alba) also involves measuring ultrasonic attenuation over a selected frequency range. Alba describes various methods of deriving particle size distributions by comparing the measured and calculated attenuation spectra.

The velocity of ultrasound in suspensions has been shown by Harker and Temple (Journal of Physics D: Applied Physics 21 (3 J8) 1576-1588) to be a complex function of volume fraction, particle radius, fluid viscosity, frequency and compressibility. The effect of particles on the velocity of ultrasound in a suspension is best explained by an example. Figure 2 shows the calculated velocity as a function of particle size for silica in water for various ultrasonic frequencies. For the larger particle sizes the wave propogation velocity is the same as that in the pure suspending fluid, although ultrasonic attenuation may be high. For the very small particle sizes, the particles tend to move in phase with the fluid in response to an ultrasonic wave. The suspension as a whole can be regarded as a continuum with respect to ultrasonic propagation. As a result, ultrasonic attenuation is very low, but the wave propagation velocity in the suspension may differ considerably from the wave propagation velocity in the pure suspending fluid. For intermediate fine particle sizes, between about 0.2 and WO 94/04907 'PCt'1U93/00419 11 microns (for frequencies 50kHz to 10MHz), there are substantial velocity differences as a function of frequency. However, these velocity differences cannot be used to determine particle size without separate measurement of solids weight fraction and fluid characteristics.

DISCLOSURE OF THE INVENTION It is an object of the present invention to provide an improved method and apparatus which avoids, or at least ameliorates, the above discussed disadvantages of the prior art. In particular, it would be desirable to measure several points on the particle size distribution curve of a suspension of alumina particles in a caustic solution of which the concentration of solute is variable. It would be especially desirable to determi.

particle size distribution on-line while avoiding the disadvantages of the prior art including the problem of scaling.

According to a first aspect of the invention there is provided a method for determining the particle size distribution of a suspension of solids in a solution bearing a solute, said method including the steps of: measuring the velocity of ultrasound on transmission through a sample of the solution; (ii) measuring the attenuation of ultrasound on transmission through the sample; J WO 94/04907 I'CfIAV93/00419 12 (iii) measuring the attenuation of Ec tromagnetic radiation on transmission through the sample to obtain a measure of the density of the sample; (iv) deriviag from the measure of density and the measure of said velocity an estimate of the concentration of solids in suspension; deriving from the measure of density and the measure of said velocity an estimate of the solute concentration; and (vi) deriving from the measures of ultrasonic attenuation, ultrasonic velocity and density a measure of particle size distribution.

Preferably, a measure of the fiaction of particles in the sample of size less than about 20 microns is derived from the measurement of the difference in velocity of ultrasound transmission at two or more frequencies through the suspension 3n combination vith the measurement of density and solute concentration.

More preferably, the ultrasound transmission of higher frequency is used to provide the measure of ultrasonic velocity and, together with the measure of density, an estimate of the concentration of solids in suspension.

Preferably also, said measure of particle size distribution obtained in stet (iv) is in respect of coarse particles only, that is, greater than about microns.

WO 94/049)07 PCr/AU93/00419 13 According to a second aspect of the invention there is provided an apparatus for determining the particle size distribution of a suspension of solids in a solution bearing a solute, said apparatus including: first means for providing a first signal indicative of the velocity of an ultrasound beam of predetermined frequency directed through a sample of the solution; second means for providing a second signal indicative of the attenuation of ultrasound on transmission through the sample; third means for measuring the attenuation of electromagnetic radiation on transmission through the sample and providing a third signal indicative of the density of the sample; fourth means for deriving fourth and fifth respective signals indicative of the concentration of solids in suspension and the solute concentration from said first and third signals; and fifth means for deriving particle size distribution from said first, second and third signals.

According to a third aspect of the invention there is provided a method for determining the solids content of a suspension of solids in a solution bearing a solute, said method including the steps of: measuring the velocity of ultrasound on transmission through a sample of the solution; (ii) measuring the attenuation of electromagnetic WO 94/04907 PC'/AU93/00419 14 radiation on transmission through the sample to obtain a measure of the density of the sample; and (iii) deriving from the measure of the density and the velocity an estimate of the concentration of solids in suspension.

According to a fourth aspect of the invention there is provided an apparatus for determining the solids content of a suspension of solids in a solution bearing a solute, said apparatus including: means for measuring the velocity of ultrasound on transmission through a sample of the solution; (ii) means for both measuring the attenuation of electromagnetic radiation on transmission through the sample and for producing a signal indicative of the density of the sample; and (iii) means for deriving signals indicative of the concentration of solids in suspension from the measurements of said density and said velocity.

According to a fifth aspect of the invention there is provided a method for determining the solute concentration of a suspension of solids in a solution bearing a solute, said method including the steps of: measuring the velocity of ultrasound on transmission through a sample of the solution; (ii) measuring the attenuation of electromagnetic radiation on transmission through the sample to obtain a WO 9Y4/04907 I'CT/A U93/00419 15 measure of the density of the sample; and (iii) deriving from the measure of density and the measure of said velocity an estimate of the solute concentration.

According to a sixth aspect of the invention there is provided an apparatus for determining the solute concentration of a suspension of solids in a solution bearing a solute, said apparatus including: means for measuring the velocity of ultrasound on transmission through a sample of the solution; (ii) means for measuring the attenuation of electromagnetic radiation on transmission through the sample and producing a signal indicative of the density of the sample; and (iii) means for deriving signals indicative of the solute concentration from the signals indicative of said density and said velocity.

Typically, the electromagnetic radiation is provided by an X-ray or gamma-ray source. The following discussion will be directed to a gamma-ray source which by no means limits the scope of the present invention.

The ultrasound can be generated by transducer(s) which may have the ability to both transmit ultrasonic waves and receive them. Generally, the frequency of the ultrasound beam is in the range of 20kHz to In a preferred embodiment, the ultrasonic WO 94/04907 PCVAAU93/00419 16 transducers are attached to probes which contact the caustic solution. These probes protect the transducers from the solution, they allow a method for the correction of electronic and transducer drifts; they allow scale growth to be monitored by measuring the transit time of ultrasonic pulses reflected from the solid/liquid interface; and they allow the transmission distance in the suspension to be varied.

In a further preferred embodiment, the ultrasonic transducers and probes and the electromagnetic radiation transmission gauge are immersed in the process stream and are therefore referred to as immersion probes.

Immersion probes have a number of significant practical advantages such as: the same probe design can be used for measurements at many different locations; the probes can be de-scaled by immersion in hot caustic; probe performance can be readily checked by immersion in standard solutions or suspensions; the probe can be calibrated by immersion in standard suspensions; and the distances between ultrasonic transmitters and receivers can be readily adjusted to achieve optimum performance.

The u'trasonic velocity can be measured by measuring the total ultrasound transit time through the suspension and probes and the probe reflection transit time of the transducers. The ultrasonic velocity Vn can be determined by the following equation: Vn Sn/(T n Rn) WO 94/04907 I'C/A U93/00419 17 where Sn is the path length in the suspension, corrected for scaling using the probe reflection transit times Rn T n is the total ultrasound transmission transit time.

In a preferred embodiment, step of the method further comprises the step of measuring the temperature of the sample. This can be achieved by placing a thermocouple into the suspension and generating a signal indicative of the temperature of the solution.

The equation for the determination of the solute concentration becomes: C a o a Vn a 2 p a 3

T

where p b b 1 ln(I/Io), ao, al, a 2 a3 bo, b 1 are constants, p is the density, I and Io are the gamma-ray intensities with and without the suspension respectively, and T is temperature.

The solids concentration W can be determined by the following equation: W c o 0 c c2V n where c 1 c 2 c 3 are constants.

Particle size distribution Dn, as defined by a plurality of solids concentrations within various size intervals can then be determined by equations involving the ultrasonic attenuation measurements at various frequencies and the gamma-ray attenuation measurement, I 1111111 WO 94/04907 IICT/A U93/004 i z 18 with corrections for the effects of caustic concentration, scaling, temperature and electronic drift. The equation used will involve linear combinations and ratios of the various measured parameters. For example, one equation for the determination of coarse particle size fractions from ultrasonic attenuation measurements at two frequencies (A and A density, velocity and temperature is:

D

n d o di (A /A2) d 2 p d3/(A 2 p) d 4 V d s

T

where d d d 2 d 3 d 4 and d are constants.

For the fine particle size fractions, equations for the particle size distributions involve ultrasonic velocity measurements at low and high frequencies as well as gamma-ray attenuation and temperature. For example, an equation for the determination of fine particle size fraction Dn from velocity measurements at low and high frequencies (V 1 and Vh), density and temperature is: Dn e0 e1 (Vh-V)!W e 2 p e 3

V

h e 4

T

where e e 2 e 3 and e 4 are constants.

The effect of scaling is corrected by using the ultrasonic probe reflection transit time and the electronic drifts are corrected by the ultrasonic probe reflection amplitude.

The above equations can be solved by entering the relevant data (or signals indicative thereof) into a

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WO 94/04907 PC'/ AU93/00419 19 programmable computer.

Typically, the solute is caustic soda and the suspension is alumina, although the invention is equally applicable to other suspensions.

The method, in a preferred form, involves the following measurements: ultrasonic transmission attenuation at a number of ultrasonic frequencies generally within the range to 20MHz (A total ultrasonic transmission transit time in the probes and suspension at each frequency (T 1 T2, ultrasonic probe reflection amplitude at each frequency (P P2 ultrasonic probe reflection transit time at each frequency

(R

1 gamma-ray attenuation in the suspension (I/Io) where I and Io are the gamma-ray intensities with and without the suspension respectively; and temperatre of the suspension Advantageously, means are included to remove or stabilise the entrained air in the sample being measured.

Agitation means may also be provided to establish and maintain substantially uniform particle suspension in the slurry.

Optionally, pulse-echo techniques rather than transmission techniques can be used. In pulse-echo WO 94/04907 PCr/A U93/004 19 20 operation, the ultrasonic transmitters are also used as receivers with sound reflector(s) being arranged opposite the ultrasonic transmitters in the measurement sections.

The advantages of preferred embodiments of the measurement system of the invention are: that analysis can be performed rapidly; measurements can be performed directly in process streams; sampling problems are minimised as a bulk analysis is made of the suspension using ultrasonic path lengths of about 50 to 300mm; the process is unaffected; and multiple points on the size distribution curve can be monitored.

BRIEF DESCRIPTION OF THE DRAWINGS A preferred embodiment of the invention will now be described, by way of example only, with reference to the following drawings in which: Figure 1 is a graph showing the calculated dependence of the absorption coefficient on particle size at different frequencies for suspensions of quartin water; Figure 2 is a graph showing the calculated velocity of ultrasound as a function of particle size and frequency for water containing 10% by weight of silica; Figure 3 is a schematic diagram of a device according to the present invent9in for on-line particle size measurement, where the device includes four pairs I WO 94/04907 PCT/AU93/00419 21 of ultrasonic transducers and a gamma-ray transmission gauge; Figure 4 is a schematic diagram of the device of Figure 3 as configured in the laboratory to determine the ultrasonic particle size analysis; Figure 5 is a schematic cross-sectional view of an immersion probe measurement system used to obtain the ultrasonic particle size analysis; Figure 6a is a cross-sectional view of the low frequency immersion probe of Figure Figure 6b is a sectional view taken along line 6b-6b of Figure 6a.

Figure 7 is a graph of particle size determined by a Malvern laser diffraction instrument versus the particle size measured by the gauge in Figures 3 and 4 for samples of 5 and 10wt% solids; Figure 8 is a graph showing the determination of particle size (d50) using the gauge in Figures 3 and 4 for alumina samples of 10 to 30wt% solids in synthetic Bayer liquors; Figure 9 is a graph showing the determination of the mass of alumina added to synthetic Bayer liquors using the gauge in Figures 3 and 4; Figure 10 is a graph showing the determination of caustic concentration using the gauge in Figures 3 and 4 for synthetic Bayer liquors, NaOH solutions and water; and WO 94/04907 PCr/AU93/00419 22 Figure 11 is a graph showing the determination of the fines fraction (1-10 microns) in six silica samples in water, each containing 10 wt% solids. Gauge determination was based on measurement of ultrasonic velocities at 250kHz and MODES FOR CARRYINC OUT THE INVENTION The invention in one preferred embodiment will now be described, by way of example only, with reference to the following examples.

EXAMPLE 1 Samples Seventeen particulate samples were used to test and demonstrate the method of the present invention. The samples comprised 7 commercially available alumina powder samples, 3 alumina trihydrate samples from Queensland Alumina Limited (QAL), 6 crystalline silica samples and 4 glass microsphere samples. The particle size of these samples were previously determined by a Malvern laser particle size analyser at the University of New South Wales. The d50 of these samples ranged from 5.9 to 210 microns.

Slurries The above samples were mixed with caustic solutions of concentrations from 150 to 250g/l NaOH and synthetic I I _I WO 94/04907 i'CT// 93/G41% 23 Bayer liquors of caustic concentrations 113 and 189g/l NaOH. The synthetic Bayer liquors had alumina to caustic ratios of 0.35 and 0.40.

Experimental Apparatus Referring to Figures 3 and 4, the above slurries 1 were placed in a stainless steel vessel 2 of 5 litre capacity as shown in Figure 3. The vessel 2 was located on a heating plate (not shown) so that the temperature cf the slurry could be raised to over 800C. Stirrers 3 and 4 in the vessel were us ed to keep the solids in suspension without introducing air into the slurry.

The apparatus included two pairs of ultrasonic transducers, a 2.25MHz ultrasonic transmitter/receiver a 2.25MHz ultrasonic receiver 6, a 10MHz ultrasonic transmitter/receiver 7 and a 10MHz ultrasonic receiver 8, which were connected to probes 9, 10, 11 ana 12 respectively which contacted the slurry 1. Machinable ceramic was found to be a suitable material for these probes, combining a low temperature coefficient for both ultrasonic attenuation and velocity with a moderate attenuation to minimise "ringing".

The apparatus also incorporated a 1 Cs gamma-ray transmission gauge 13 having a 370 mBq 137 Cs radioisotope source 14, a lead shield 15 and a NaI(Tl) scintillation detector (50 x 50mm) 16 coupled with a photomultiplier tube 17. A thermocouple 18 was also placed into the slurry to measure the temperature

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WO 94/04907 I'Cr/AhU93/00419 24 of the suspension.

Signals were generated by the generator/pulsers, 19 and 20 as shown in Figure 4 and transmitted through the slurry 1. Attenuated signals were then received by the transducers, 5, 6, 7 and 8 and amplified by amplifiers 21, 22, 23 and 24, digitised by digitisrs 25, 26, 17, 28 and fed into a computer 29. Gamma-rays were also transmitted from source 14 ard detected by the scintillation detector 16, the photo.":ltiplier tube 17 being powered from high voltage source 30. The signals thus detected were then fed through a preamplifier 32, a gain-stabilised amplifier 32, a single channel analyser 33 and fed into comput 29. Temperature was also measured using the thermocouple 18 and the temperature values 34 were also fed into computer 29.

Results In the first set of experimental data, 14 samples (e-..,luding the three QAL samples) were measured in caustic solutions over a range of caustic concentrations (150 to 250g/l), solid fractions (5 to 20wt%) and temperatures (22 to 35 0 This first data set comprised 80 sets of measurements.

The accuracy of determination of particle size sample mass and caustic concentration is given in Table 1 and Figure 7. The results show that d50 can be measured to within 5.9pm (one standard deviation) provided that the solids fraction is below about 12wt%.

NVO 94/04907 I)C/AU9300419 25 The errors in particle size determinations would be lower for a less diverse range of samples to those used in the present experiments.

TABLE 1 Range of Conditions in Laboratory Experiments d50(pm) Caustic Solids (g/l NaOH) fraction (wt%) Parameter Rms error 3.8im 33-98 113-188 10-30 5.9pm 7-210 150-250 5-10 0.97 wt% 91-100 wt%* 113-250 24-30 Caustic 1.32 g/1 33-98 113-188 3-30 3.78 g/l 7-210 150-250 5-20 Solids 0.49 wt% 33-98 113-188 3-30 fraction 0.68 wt% 7-210 150-250 5-20 Range of fraction above 40 pm (wt%) In a second set of experimental data, three alumina hydrate samples were measured in four synthetic Bayer liquors at solids fractions from 3 to 30wt%. The results of these measurements are shown in Table 1 and in Figures 8 and 9. In Figure 9, a mass of 1.8 kg is equivalent to a solids fraction of The results for particle size (d50) show that can be determined to within an rms error of 3.79pm for solids fractions between 10 and 30wt%. Including the WO 94/04907 I)C/AU93/004199 26 points at 6 and 9wt% solids increases the rms error to Alternatively, the particle size data can be analysed in terms of the fraction greater than a particular size. Analysis of six samples with between 91% and 100% greater than 40 microns showed that the fraction greather than 40 microns could be determined to within 0.97wt% for the range of conditions shown in Table 1.

The results for the determination of caustic concentration based on ultrasonic velocity and y-ray density show that for the synthetic Bayer liquors alone, caustic concentration can be determined to within 1.17g/l. Combining all the solution runs no particulates) on synthetic Bayer liquors, caustic and water shows that the caustic concentrations can be determined to within 5.47 g/l (Figure Ultrasonic velocity is strongly affected by caustic concentration. For example, at 200g NaOH per litre, a 2g/l increase in caustic concentration increases the velocity of ultrasound by 2.2m/s. However, ultrasound velocity is not strongly affected by temperature, the change being only about -0.6m/s per oC at 2.25MHz and -0.44m/s per oC at Typical terms in the equations used to determine particle size, solids fraction and caustic concentration are given in Table 2.

WO 94/04907 PCT/AU93/00419 27 TABLE 2 Parameter (Y) Typical Solids Particle Particle Caustic terms in fraction or size (d50) size Concentration equation* sample mass than Xz P AIA 2 Az/A 2

P

X2 V 1 1/(A 2

V

X

3 A, V 1

X

4

V,

*The parameters were determined using equation so the form Y a o a X a2 X a 3 a X 4 where.

a a are constants and X X 4 are listed in the Table. A A 2 corrected ultrasonic amplitude at 2.25 and 10MHz respectively and V measured velocity of 2.25MHz ultrasound in the suspension.

EXAMPLE 2 An additional set of measurements were obtained to examine the feasibility of using ultrasonic velocity techniques to determine fine fractions independent of the larger size fraction concentrations. Laboratory experiments were carried out using six silica samples with fractions finer than 10 microns ranging from 20 and 53 wt%. The samples were mixed with water at solids loadings of 5, 10 and Ultrasonic velocities were measured at the WO 94/04907 PCT/AU93/00419 28 frequencies of 250kHz and 10MHz to determine the fines fractions in the samples. The results obtained are illustrated graphically in Figure 11 and are accurate to better then 3wt% for constant solids loading. This error rises to approximately 5wt% for variable solids loading.

In agreement with the calculated values displayed in Figure 2, the velocity of the 10MHz ultrasound at constant solids fraction was essentially constant for the varying particle size while the velocity of the 250kHz ultrasound decreased substantially linearly with increasing fine fraction.

Referring now to Figures 5, 6a and 6b there is illustrated a schematic representation of a measurement system 45 as envisaged by the present invention. The system includes a tank 46 having an inlet and outlet 47 and 48 through which a sample 49 flows prior and subsequent to measurement.

System 45 also includes a stirrer 50 which is disposed near the base of tank 46 and driven by a motor 51 for maintaining a well mixed solution within the tank. Two immersion probes 52 and 53 extend downwardly into the tank and include respective support tubes 54 and 55, and sensor portions 56 and 57. Preferably, portions 56 and 57 are disposed approximately mid-way between the top and base of tank 46, however, satisfactory operation is achieved while these portions

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WO 94/04907 PC/AU93/00419 29 are completely immersed in sample 49. Probes 52 and 53 are respectively configured to measure low and high frequency ultrasound velocity through the sample.

An enlarged cross-sectional view of probe 53 is illustrated in Figures 6a and 6b. Sensor portion 57 includes two axially spaced apart tubular bases 60 and 61 which are connected by way of four peripherally located and axially extending tubes 62. Base 61 includes a centrally mounted radioactive source 63 contained within a storage shield 64. Opposing source 63 is a gamma ray detector 65 located within base Base 61 also includes four equally angularly spaced ultrasonic transducers 66 which are radially offset from source 63. Base 60 includes four similar transducers 67 which are each disposed immediately above one of respective transducers 66.

It will be appreciated that tube 62 preferably communicates with the interior of both bases 60 and 61 so that any water or power supply lines can extend therethrough. Preferably also, the cables carrying the signals provided by transducers 66 are also ducted through one of tubes 62.

It will be understood that the velocity of ultrasound transmission through a sample can be measured in other ways without departing from the scope of the invention. The velocity can be compared with the velocity obtained using calibration samples or the WO 94/04907 P(/AU93/00419 30 caustic concentration can be calculated from a knowledge of the constants preferably by use of analogue or digital computation equipment.

Likewise the density measurements can be derived from the y-radiation attenuation by calibration or by calculation from a knowledge of the constants.

Although the foregoing describes specific embodiments of the invention, other modifications apparent to the skilled addressee fall within the scope of the invention.

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Claims (14)

1. A method of determining the particle size distribution of a suspension of solids in a solution bearing a solute, said method including the step of: measuring the velocity of ultrasound on transmission through the sample; (ii) measuring the attenuation of ultrasound on transmission through the sample; (iii) measuring the attenuation of electromagnetic radiation on transmission "through the sample to obtain a measure of the density of the sample; (iv) deriving from the measure of density and the measure of said velocity an estimate of the concentration of solids in suspension; deriving from the measure of density and the measure of said velocity an estimate of the solute concentration; and (vi) deriving from the measure of ultrasonic attenuation, ultrasonic velocity and density the measure of particle size distribution.

2. A method according to claim 1, wherein the temperature of the sample is variable, said method further including the step of measurement of the temperature of the sample.

3. A method according to claim 1 or claim 2 wherein a measure of the fraction of particles of size less than 20im in the sample is derived from a measurement of the difference in velocity of ultrasound transmissions at two or more respective frequencies through the suspension in combination with the measurement of density and solids concentration. )7107.80 orC/mja I -32-

4. A method according to claim 3 wherein the ultrasound transmission of higher frequency is used to provided the measure of ultrasonic velocity and together with the measure of density, an estimate of the concentration of solids in suspension.

A method according to any one of claims I to 4 wherein the ultrasonic velocity is measured by obtaining the ultrasound transit time and probe reflection transit time from spaced apart ultrasonic transducers.

6. A met 1 rding to any one of claims 1 to 5 wherein the solute is caustic soda.

7. A method according to any one of claims 1 to 6 wherein the solid is alumina.

8. An apparatus for determining the particle size distribution of a suspension of solids in a solution bearing a solute, said apparatus including: S...first means for providing a first signal indicative of the velocity of an ultrasound beam of predetermined frequency directed through a sample of the solution; second means for providing a second signal indicative of the attenuation of ultrasound on transmission through the sample; third means for measuring the attenuation of electromagnetic radiation on transmission through the sample and providing a third signal indicative of the density of the sample; fourth means for deriving fourth and fifth respective signals indicative of the concentration of solids in suspension and the solute concentration from said first and third signals; and fifth means for deriving particle size distribution from said first, second and third signals. 1711 $7.n nocil/mja -33-

9. An apparatus according to claim 8 wherein said first means also provides a sixth signal indicative of the velocity of another ultrasound beam of differing frequency for providing a measuie of the fraction of particles in said sample of a size less than about microns.

10. An apparatus according to claim 9 wherein said fifth means derives the fraction of particles in said sample of size less than about 20 microns from a measure of the difference between a plurality of first signals, said third signals and said fourth signal, wherein the predetermined frequency of the beam differs for each of said first signals.

11. An apparatus according to claim 10 wherein said predetermined frequency is greater than said differing frequency.

12. A method for determining the solids content of a suspension of solids in a solution bearing a solute, said method including steps of: measuring the velocity of ultrasound on transmission through a sample of he solution; of the solution;

17107.80 nocn.mja WO 94/04907 PCT/AU93/00419 34 (ii) measuring the attenuation of electromagnetic radiation on transmission through the sample to obtain a measure of the density of the sample; and (iii) deriving from the measure of the density and the velocity an estimate of the concentration of solids in suspension.

13. An apparatus for determining the solids content of a suspension of solids in a solution bearing a solute, said apparatus including: means for measuring the velocity of ultrasound on transmission through a sample of the solution; (ii) means for both measuring the attenuation of electromagnetic radiation on transmission through the sample and for producing a signal indicative of the density of the sample; and (iii) means for deriving signals Indicative of the concentration of solids in suspension from the measure of said density and said velocity.

14. A method for determining the solute concentration of a suspension of solids in a solution bearing a solute, said method including the steps of: measuring the velocity of ultrasound on transmission through a sample of the solution; (ii) measuring the attenuation of electromagnetic radiation on transmission through the sample to obtain a measure of the density of the sample; and WO 94/04907 PC/AU93/00419 35 (iii) deriving from the measure of density and the measure of said velocity an estimate of the solute concentration. An apparatus for determining the solute concentration of a suspension of solids in a solution bearing a solute, said apparatus including: means for measuring the velocity of ultrasound on transmission through a sample of the solution; (ii) means for measuring the attenuation of electromagnetic radiation on transmission through the sample and producing a signal indicative of the density of the sample; and (iii) means for deriving signals indicative of the solute concentration from the signals indicative of said density and said velocity. M