Minerals Engineering, Vol. 11, No. 11, pp.

1081-1087, 1998
O 1998 Elsevi~ Science Ltd
Pergamon All right8 reserved
0892...6875(98)00094-6 0892-6875~tS - - see from matter

MICROWAVE TREATMENT OF MINERALS---A REVIEW

S.W. KINGMAN and N.A. ROWSON

School of Chemical Engineering, University of Birmingham, Edgbaston, Birmingham BI5 2TT, UK

E-mail: swk575 @novell3.bham.ac.uk
(Received 24 March 1998; accepted 13 July 1998)

ABSTRACT

This paper presents a review of the advances in the microwave treatment of minerals from
the early stages of development to possibilities for future utilisation. Many different
applicativns are considered, including fundamental heating rate studies, microwave
assisted grinding, possible exploitation in the area of extractive metallurgy and also
microwave treatment of coal. Conclusions are presented regarding the need for further
fundamental and pilot scale data. Further indications of the potential for the commercial
exploitatitm of microwaves within the mineral processing and extractive metallurgical
industries have been included.

Keyworct~
Mineral Processing; Extractive Metallurgy; Ore Mineralogy; Mineral Economics.

INTRODUCTION

Microwaves are a form of electromagnetic energy with associated electric and magnetic fields. The materials
which couple with (absorb) the microwave radiation are termed dielectrics and contain dipoles. When the
microwaves are applied to dielectric materials the dipoles align and flip around since the applied field is
alternating. Subsequently, the material heats when stored internal energy is lost to friction.

From a commercial standpoint the microwave oven was first developed in 1951 when a large floor standing
model was produced by the Raytheon company of North America [ 1]. For domestic purposes ovens became
available in the earZly 1960's and thus a mass market was initiated. It was not long after this that industrial
applications began to be considered and the first of these included rubber extrusion, plastic manufacture,
and the treatment of foundry core ceramics. In the mid 1970's the international oil and gas shortage led
to an escalation in energy costs, this led to an increased research effort into the applications of microwave
radiation. In 1978 2'avitsanos [2] obtained a U.S. patent for the desulphurisatlon of coal using microwaves,
this was the first recorded attempt to expose minerals to microwave radiation. It was not until 1984 that
interest was renewed with the publication of the pioneering paper by Chen et al. [3] concerning the relative
transparency of minerals to microwave energy.

1081
1082 S.W. Kingmanand N. A. Rowson

INITIAL RESEARCH IN THE M I C R O W A V E TREATMENT OF MINERALS

The research produced by Chen et al. although qualitative in nature was the first attempt to assess the
heating rates of different minerals within a dielectric field. Forty minerals (purity -99%, mass 0.5-1g) were
exposed to microwave energy in order to ascertain their response. Difficulties were reported in making
accurate temperature measurements within the microwave cavity, therefore, the results are reported as a
series of observations. Attempts were made to measure temperature using infra-red camera techniques,
however, this method was considered to be inaccurate due to its inability to measure core temperature. From
the results of the study it was concluded that: most silicates, carbonates and sulphates, some oxides and
some sulphides were transparent to microwave radiation, however, most sulphides arsenides, sulphosalts and
sulphoarsenides heated strongly, emitting fumes and fusing. Although it is appreciated that this was a
fundamental investigation, some indication of temperature increase per unit volume of sample would have
been a useful addition to the study.

The problems of temperature measurement in microwave treated samples were addressed by Walkiewicz
et al. [4] by the completion of a more detailed, quantitative study of the microwave heating characteristics
of various minerals and compounds. The materials selected were irradiated in a lkW, 2.45 GHz heater and
the resulting temperatures and rates of heating determined (See Table 1). In this study the problem of
temperature measurement was overcome using a metal sheathed thermo-couple. The thermocouple was in
constant contact with the sample. It is stated that measurements on boiling water showed the system to be
accurate to within 2%. A sample mass of 25g was utilised for all tests, except for low density minerals
where a constant volume of 18ml was used. The results obtained were similar to those of Chen et al i.e.
certain groups of minerals could be identified as good heaters and others as poor heaters. Another important
observation reported was that the rapid heating of ore minerals within a non-absorbing matrix generated
thermal stresses, this caused cracking which was both transgranular and intergranular in nature. The study
concluded that some indication had been given to potential applications of microwave energy in mineral
processing. However, in considering the feasibility of large scale processing, it was stated that industrial
application may be limited not by accessibility of equipment but rather by their cost.

TABLE 1 Snmmary of Heating Results (After Walkiewicz 1988)

MINERAL CHEMICAL MAX TEMP TIME

COMPOSITION ACHIEVED (C) (MIN)
CHALCOPYRrI'E CuFeS 2 920
GALENA PbS 956 7
MAGNETITE Fe304 '1258 2.75
ORTHOCLASE KAISiO30 s 67 6
PYRITE FeS 2 1019 6.75
QUARTZ SiO 2 79
SPHALERITE ZnS 88

McGill et al. [5] discussed the effect of power level on mineral heating rate. Minerals similar to those
utilised in previous studies were powdered and exposed to various microwave power levels ranging from
500 to 2000 W. All tests exploited 25g samples or an approximate volume of 12-14g for low density
minerals. It was observed that in general, an increase in power led to an increase in the heating rate of the
mineral. However, this was only true, for the minerals which had previously demonstrated an affinity for
microwave radiation. Low loss materials such as quartz and orthoelase did not heat effectively, regardless
of the applied power.

The above studies whilst few in number constitute the majority of the early research in this field of interest.
Many of the subsequent papers dealing with the applications of this technology utilise the theories presented
here without question. It could be stated that a lack of fundamental data concerning the interactions between
microwave radiation and minerals is a hindrance to the implementation of the technology.
 Microwave treatment of minerals 1083

THE APPLI[CATION OF MICROWAVES IN THERMALLY ASSISTED LIBERATION

The application of thermal energy to assist with mineral liberation has been studied since the start of the
century with Yate:~ [6] and Holman [7] both completing studies into the effects of heating on rock fracture.
Typically, ores contain minerals which have very different mechanical and thermal properties. When energy
is applied, stresses of different magnitudes can be created within the lattice, both by the heating and cooling
processes. This is due to significantly different thermal expansion coefficients existing between different
mineralogical species The stresses lead to localised fractures of an intergranular and transgranular nature
but not necessarily to catastrophic failure. Fitzgibbon and Veasey [8] suggested these fractures may lead
to a significant reduction in grinding resistance, however the benefits of thermal pre-treatment were
economically unsound. It was suggested, however, that utilisation of microwave energy may improve the
process economic,,;.

Thermally assisted liberation using microwaves to provide the energy input rather than conventional methods
was considered f t ~ e r in 1991, with the publication of "Microwave Assisted Grinding" by Walkiewicz et
aL [9]. Iron ore samples were subjected to 3kW, 2.45 GHz radiation and their temperature raised to between
840 and 940C. S.E.M photomicrographs confirmed fractures along grain boundaries and throughout the
gangue matrix. St~mdard Bond grindability tests showed that the microwave treatment reduced the work
index of the iron o~resby between 10 and 24%. It was concluded that while a reduction in work index alone
could not justify the use of microwave thermally assisted liberation other benefits coupled with it may.
These additional benefits include; less wear of the mill, the mill liner and the milling medium. Improved
grindability would also result in an increased throughput, and the amount of any recycled ore would be
reduced. However, the most important benefit would be the cleaner liberation of the valuable mineral
particle which wotLldimprove the concentrate grade and metal recovery after beneficiation. A recent study
[ 10] by EMR Microwave Technology Corp., has considered the application of microwaves to refractory gold
concentrates at a pilot scale. A process has been developed which applies microwaves to the concentrate
via a fluidised becl reactor. With pyritic ores the pyrite is converted to hematite and elemental sulphur
causing liberation of the gold. The hematite can be directly leached and the sulphur sold as a by product.
The system has the added environmental benefit of producing virtually no sulphur dioxide. Based on the
findings of pilot scale tests it is estimated that for a 2000t/day operation producing 200t/day of concentrate,
the process could reduce total operating costs to US$8.60/t compared to US$33.58/t using pressure oxidation
and US$13.74/t for roasting. It is also suggested that capital costs for microwave processes would he lower
as the plant does not have to cope with high temperatures and pressures. A 200 t/d pretreatment plant using
the microwaves prcCess would cost an estimated US$ 3.84 million compared to US$ 6.9 million for roasting
and US$ 26.5 million for pressure oxidation. It is estimated that by using the microwave process costs could
be cut by US$ 50/oz.

Kingman and Rowson [11] considered the effect of microwave energy upon the processing of a massive
Norwegian ilmenite ore. It was found that large reductions in Bond work index could be obtained after
exposure to microwave energy for short periods of time. By replicating the plant flowsheet for the ore,
increases in grade and recovery of ilmenite were also presented, again for microwave treated samples. It
was suggested that the increases in grade and recovery coupled with that of a reduction in Bond work index
and the associated benefits already considered would make the application of microwave energy to this ore
economically favourable. However, a full techno-economic analysis was not presented.

A further study by Walkiewicz et al. [12] considered the effect of temperature and power level on Bond
work index. A Taconite feed material was heated to various temperatures at both 12 and 16kW. Improved
values of grindabilJity were obtained at all power levels which confirmed the hypothesis that microwave
energy can induce thermal stress cracking. A comparison was also made between material heated to 880C
by microwave radiation and material heated to 197C. It was found that ore heated to the lower temperature
showed a considerable decrease in Bond work index and this significantly improved the cost effectiveness
of microwave assisl~! grinding when compared to the sample heated to 880C.
1084 S.W. Kingman and N. A. Rowson

APPLICATIONS OF MICROWAVE RADIATION IN EXTRACTIVE M E T A L L U R G Y

In 1986 Worner et al. [13] considered the applications of microwave energy for pyrometallurgy. It was
demonstrated that microwave energy had considerable potential for both ferrous and non ferrous smelting
and also across the whole spectrum of commercial metal production from tin to tungsten. Various roles for
the microwave energy were suggested, however, most of these utilised the microwave radiation either for
the application of energy to smelting processes or for the drying (or sintering) of materials. Following this,
Standish and Worner [14] considered the applications of microwave energy for the reductions of metal
oxides with carbon i.e. ironmaking. Identical samples of hematite ore fines, coke dust and lime powder were
placed in a crucible and compressed. Certain samples were reduced conventionally at 1000C and others
were reduced in a microwave oven operating at 1.3kW and with a frequency of 2.45GHz. In both cases
weight loss as a function of time was measured, using identical thermogravimetric methods. Those samples
which had been microwave treated showed an increase of approximately 16% in weight loss over those
conventionally treated. Several advantages of microwave reduction were suggested the most important being
that microwaves heated volumetrically i.e. no "cold centres" occurred in treated ore.

Various authors have considered the applications of microwave energy to the extraction of gold. Woodcock
et al. [15] discussed the possibilities of using microwave energy in the extraction of gold, both as a pre-
treatment or during conventional processing techniques. The effect of microwave energy upon the different
mineralogical forms of gold, certain generic flowsheets and also specific extraction processes were
considered. It was felt that microwaves offered most potential in roasting refractory concentrates. Haque
[16] applied high power microwave energy to typical refractory gold concentrates. It was found that
microwave treatments were highly effective in calcination of the concentrate, especially for particles of 2mm
or below. Particles larger than 2ram suffered from incomplete calcination. Identical 50g samples of
concentrate were roasted in air at 550C (a lower temperature than for conventional roasting). It was found
that more than 80% of the arsenic and sulphur were volatilised off as As203 and SO3 respectively, and iron
was oxidised to hematite. Cyanidation of the resultant calcine extracted 98% of the gold.
Kelly and Rowson [17] considered the novel microwave reduction of pre-oxidised Ilmenite concentrates.
The oxidation and reduction of iron in ilmenite concentrates between the ferric and ferrous states has been
found to greatly increase its chemical activity. Two ilmenite concentrates were first oxidised in a
conventional muffle furnace at 1000C. The ferric iron was then reduced back to ferrous iron by heating
with a fine carbon powder under an inert nitrogen atmosphere. The reduction process was carried out in a
variable power (0-1500kW), 2.45GHz microwave oven. Duplicate control samples were reduced at
temperatures over the range 700-1000C. After reduction the effects of reduction on phase change, surface
morphology and leachability were determined. It was shown that broadly similar results were obtained for
both microwave treated and conventionally treated samples i.e. almost total reduction could be achieved in
a microwave oven over a very short period of time (typically 8mins at 750W compared to 8hrs at 800C).
The authors suggested that the extraction of iron and titanium from microwave reduced samples increased
with the extent of reduction i.e. exposure time. Surface areas and thus porosities were also shown to
increase with the extent of the reduction. Dissolution characteristics similar to those obtained by
conventional reduction were also demonstrated. A final conclusion stated that with higher power microwave
radiation and increased exposure times, iron would be totally reduced to the ferrous state. This would mean
that the same results would be obtained as for conventionally reduced samples, however, much more
efficiently.

T H E O R E T I C A L STUDIES IN T H E MICROWAVE T R E A T M E N T OF MINERALS

Little research has been instigated in the theoretical aspects of microwave treatment to minerals. What little
work carried out lies in two main areas: firstly, prediction of mineral heating rate in an applied dielectric
field and secondly, the modelling of thermal stresses within irradiated mineral matrices.

Church et al. [18] conducted research to determine if microwave heating can influence the response of a
particular process to enhanced mineral beneficiation. In order to do this the authors calculated the dielectric
constant (c.r) (also known as the relative permittivity) and the loss tangent (tank). From these data a
 Microwave treatment of minerals 1085

theoretical heating model was developed to predict the amount of microwave radiation absorbed during the
heating process. The model was then used to show that different minerals had different heating rates which
may selectively modify the chemical or physical properties of one of the constituents, thereby enhancing
the potential for mineral separation.

Salsman et al. [19'] used a finite element numerical model to predict the thermomechanical response of a
single pyrite particle in a calcite host rock during microwave treatment. They predicted that a significant
temperature differential would occur between the two phases and the resulting thermomechanical stresses
would far exceed the typical strengths of these materials, thus, suggesting a reduction in work index. It was
postulated by usir~g short (less than 1 second) pulses of very high power energy that the economics of
microwave assisted grinding could be drastically improved.

THE MICROWAVE TREATMENT OF COAL

Considerable resem'ch has been undertaken into the effect of microwave radiation upon coal. Microwave
treatment of coals can be classified into three main sections; Heating rate investigations, Desulphurisation,
and grindability studies.

Zavitsanos [2] studLiedpower absorption at various frequencies on coal/pyrite mixtures. This work concluded
that frequencies of 5 GHz gave the greatest differential heating between pyrite and coal, however, the
standard microwave frequency of 2.45 GHz produced good results. Bluhm [20] reported similar observations
but noted that improved differential heating could be achieved at higher frequencies.

Various authors have suggested the use of microwave radiation in the desulpurisation of coal. Viswanathan
[21] showed that by the selective heating of pyrite to pyrrhotite, the sulphur content of a typical British coal
could be reduced by 24% and the ash content by 22.6%. It was also suggested that since pyrrhotite is
significantly more magnetic (100) than pyrite, conventional magnetic separation could be employed in the
cleaning process, and also in the short term selective demineralisation of coals was a real prospect. Rowson
and Rice [22] and Hayashi et al. [23] investigated the role of caustic leaching during the microwave
desulphurisation of coals. Molten caustics (NaOH and KOH) were shown to be effective absorbers of
microwave radiation and led to the accelerated differential heating of coal/pyrite phases. This was especially
true in low pyrite Igrade coals where little heating would normally occur. Sixty percent reductions in total
sulphur content are typically reported.

The production of pulverised coal feed for coal fired power stations is a highly energy intensive process,
an estimated 4x109 kWh annual for the U.S alone. Harrison and Rowson [24] demonstrated that a reduction
of 30% in the comparative work index could be achieved using a 650W 2.45GHz microwave source. The
reduction in relative work index occurring because of cracking initiated around pyrite grains and
superheating of w.'Lter in the porous coal structure. It was concluded that as well as a reduction in work
index some additional desulphurisation had occurred thus improving the economic and environmental
benefits of the work.

A review by Row:son [25] of research carried out by the General Electric Company of North America
considered pilot sc~de microwave desulphurisation studies. Microwave conveyor systems operating at 15kW
were used to treat run of mine coal. The microwaves were found to selectively heat the pyrite in the coal
causing the formation of pyrrhotite. It was stated that pyrrhotite could be removed by low intensity magnetic
separation. The quoted treatment cost per tonne of coal was $22, this compared most favourably to
traditional technologies such as flue gas desulphurisation which had a treatment cost of $26 per tonne.
1086 S.W. Kingmanand N. A. Rowson

CONCLUSIONS

Although the quantity of research carded out in this field is limited the results published to date indicate
that the future for applications of microwave energy within the mineral industries is encouraging.
Microwave assisted grinding has produced particularly good results. With further work involving higher
power levels and shorter exposure times, the benefits of these techniques could be established categorically.
This includes the possibility of treating low grade and complex ores where liberation at present is difficult
to accomplish economically. The use of microwave radiation for the desulphurisation of coal displays
potential and may soon be a commercial reality. This would allow the use of high sulphur coals in an
environmentally and economically sound way. A number of applications for microwave technology have
been reviewed in this paper. In general, these studies have been exploratory in nature and have also been
performed on a laboratory scale, however, the results of the pilot scale tests mentioned give encouraging
results when microwave utilisation is compared to more traditional technology.

To advance the application of microwave energy in the minerals industry certain further research is required.
The role of the research sectors will be to provide the underpinning science of the fundamental interactions
within these processes. Several key areas of research are required:-

i) Minimalisation of energy input into the ore.

ii) Frequency optimisation for maximum heating efficiency.
iii) Data concerning the effects of sample temperature on dielectric constants.
iv) Scale up to tonne/hr systems.

ACKNOWLEDGEMENTS

The authors wish to thank EPSRC, Rio Tinto Technology Development Ltd and the University of
Birmingham for funding this research.

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 Microwave treatment of minerals 1087

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