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Hydrometallurgy 59 2001. 217231 www.elsevier.

nlrlocaterhydromet

The design of bioreactors


G. Rossi )
Dipartimento Geoingegneria e Tecnologie ambientali, Uniersita ` degli Studi, Piazza dArmi, 19, 09123 Cagliari, Italy Received 19 October 1999; accepted 24 March 2000

Abstract A survey of the literature on biohydrometallurgical topics revealed that the papers devoted to bioreactors amount to less than 5% of the total and refer mainly to the analysis of the performance and to design guidelines of stirred tank and of bubble column machines, the so-called Pachuca tanks. These machines can be defined conventional in the sense that they have been borrowed from chemical engineering and hydrometallurgy and adapted to the requirements of biohydrometallurgical processes. However, past experience has shown that these types of reactors do not fully match the very particular conditions that exist in biohydrometallurgical systems that, quite correctly, have been qualified as AhybridB owing to their specificity since they are characterized by many of the features of hydrometallurgical operations and of biological conversions. Literature data and the authors personal experience demonstrate that one of the present major drawbacks of these reactors is the power requirement that seriously affects the competitiveness of biohydrometallurgy with pyrometallurgy. The factors affecting the performance of biohydrometallurgical reactors are discussed with special reference to the process parameters and an analysis of the conditions to be satisfied by an ideal bioreactor is carried out. In the light of these considerations, the reactors currently operating in commercial plants are examined. The new prospects opened up by recent developments are finally discussed and, also on the grounds of experience recently gained on a laboratory scale, the potentials of machines tailor-designed for the conditions reigning in biohydrometallurgical systems are outlined. q 2001 Elsevier Science B.V. All rights reserved.
Keywords: Bioreactor; Biorotor; Stirred tank reactor; Pachuca; Solubilization rate; Design; Mass transfer coefficient

1. Introduction Compared to the great effort devoted worldwide to the biology and physiology of microorganisms and to biosolubilization kinetics in the light of microberminerals interactionswhere the influence of reactors has unfortunately been overlookedthe

Tel.: q 39-070-675-5528; fax: q 39-070-675-5523. E-mail address: grossi@vaxcal.unica.it G. Rossi..

published results of investigations on reactors suitable to biohydrometallurgical processes only represent a small minority. In fact, out of the total number of papers published in the volumes of Symposia Proceedings and in the journals over the years, not even 5% have been devoted to bioreactor technology. Most of these papers provide very good design guidelines, and an indication of the excellent cultural and practical background of the authors in chemical engineering. However, they are based on the implicit

0304-386Xr01r$ - see front matter q 2001 Elsevier Science B.V. All rights reserved. PII: S 0 3 0 4 - 3 8 6 X 0 0 . 0 0 1 6 1 - 4

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G. Rossi r Hydrometallurgy 59 (2001) 217231

assumption that the microflora is kind of a biological catalyzer, whose overall performance is only moderately dependent on the operating characteristics of the machines where the process is carried out. In my mind this is probably the Achilles heel of this approach. Hence, the reason to review and develop the subject of biohydrometallurgical reactor design was the desire to discuss the state of the art and to point to the need for further research aimed at providing our technology with suitable machines where the potential of biohydrometallurgy can be fully exploited.

3. The factors affecting biohydrometallurgical reactor performance Biohydromellurgical processes take place in three-phase systems, consisting of i. an aqueous phase, that is a solution of salts providing the nutrients for a microflora that acts as a biological catalyzer of the metal sulphides oxidation processes, ii. a solid phase, consisting of the finely ground ore that contains a mixture of waste rock and metal values combined with sulfur to form sulphides, and iii. a gaseous phase consisting of a mixture of atmospheric oxygen and carbon dioxide. The aqueous phase is the suspending medium where several elementary processes occur: a. the growth of microorganisms, b. the encounter of solid particles with microorganisms, c. the encounter of solid particles with chemically active molecules, d. the release of metal ions, e. the uniform distribution and effective dissolution of oxygen and carbon dioxide. The solid phase is the energy source for microbial biosynthesis, i.e. for microbial growth and continuously releases metal and sulphur ions in oxidized form. The gaseous phase supplies the oxygen required for the oxidation processes as well as the carbon dioxide that the microflora uses for its biosynthesis w4x.

2. Expected performance of biohydrometallurgical reactors Biohydrometallurgical processes are very attractive insofar as they present few environmental hazards. However, they are still a long way from being able to compete with pyrometallurgical and pressure leaching processes mainly because of the unsatisfactory all-round performance of the reactors, the devices where the process is carried out. The performance of a reactor is considered economically convenient whenfor comparable qualitative and quantitative characteristics of the end productthe incidence of the investment and operation costs on the unit productin our case the tonne of metal solubilized and recoveredis reasonably lower than the expected returns and, in any case, is lower than that of other processes. The parameters for assessing the biohydrometallurgical performance of a reactor for a given production are i. tank size related to the dry mineral throughput, ii. total power requirements, i.e. the power for mixing and aeration, referred to the unit mass of metal recovered in unit time in bioleaching or to the unit mass of sulphur removed in unit time in biodesulphurization, iii. the chemical compounds added to the aqueous phase as nutrients for the microflora or as pH modifiers, iv. plant attendance and supervision, v. effluents purification and vi. maintenance. The first parameter affects investment costs, the other five determine operating costs. These costs are of the same order of magnitude w13x.

4. The general design procedure of a biohydrometallurgical reactor The design procedure shown in the block diagram of Fig. 1 is based on the well documented expected performance of a biohydrometallurgical reactor. The inputs are represented by the AproductionB and Akinetic dataB. At this juncture it should be stressed that in effect, the real independent outputs are the production data, insofar as the kinetic data are strongly dependent upon reactor type and environment. This has been highlighted in recent papers w5,6x and justifies the AfeedbackB line linking the AType of reactorB box to the AKinetic dataB box. In fact, the microflora is more than a simple catalyzer. In conventional chemical engineering processes the amount of catalyzer does not vary with time, whereas in biohydrometallurgical processes the microbial populationwhose growth has been described as a Apseudo autocatalytic processB may vary with time

G. Rossi r Hydrometallurgy 59 (2001) 217231

Fig. 1. Logical diagram for the design of a biohydrometallurgical reactor.

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depending on the conditions reigning in the bioreactor. The faster the microbial growth kinetics, the faster the oxidation and solubilization process. The most important factors influencing microbial growth are oxygen availability, determined by its mass transfer coefficient, and substrate availability, that depends upon the exposed mineral surface, both achieved by adequate mixing. The most significant factors adversely affecting microbial growth are the shear stresses within the suspension, the accumulation of metabolites, incorrect temperature and hydrogen ion concentration of the aqueous phase and the release of toxic substances by the surfaces minerals and equipment. with which the suspension comes into contact. The reactors most commonly employed in biohydrometallurgical processes are the Stirred Tank Reactor STR., and the Air Lift Reactor ALR. Pachuca tank. w7x. Other reactors have been proposed recently but are dealt within a separate section as they can be regarded as typical examples of possible developments of bioreactors tailor-made for biohydrometallurgy. As a specific design procedure has to be followed for each type of reactor, in the following sections the main types of reactors will be considered separately. Some time ago it was suggested that the plug-flow reactor is the most suitable to the type of reactions occurring in metal sulphide bioleaching w4,810x. However, on account of the almost unsormountable practical problems that arise with this type of reactor, it has to be simulated by a cascade consisting of a suitable number of vessel reactors. It has been shown that at least six vessels are required w4,11x as a smaller number results in short-circuiting of the suspension with loss of effectiveness. 4.1. The stirred tank reactor (STR) This reactor, borrowed from chemical engineering, has been given priority since the early days of biohydrometallurgy, in spite of the evident drawbacks that have emerged in biohydrometallurgical applications. A very interesting technico-economic analysis, carried out by one of the European partners in the coal biodepyritization pilot plant project at Porto Torres Sardinia, Italy., funded by the Com-

mission of European Communities, produced evidence that, as far as the achievement of the desired levels of mass transfer, mixing and suspension is concerned, the STR performs better than the Pachuca tank R. Meester, pers. written commun., 1992.. The experimental data reported by Acevedo and Aroca w12x also show the STR to be superior in this sense. The most important role is played by the impeller, which has to accomplish three major tasks, solids suspension, mixing and dissolution of the required atmospheric oxygen into the aqueous phase, maximizing the interfacial area between the gaseous and aqueous phases. Initially, and for many years, the Rushton-type turbine was the most widely used impeller for these reactors, but lately the curved blade, axial flow impeller has been shown to outperform the Rushton turbine as it requires less power for achieving the same performance and induces smaller shear stresses in the suspensions w13,14x. Chemical engineering has provided some correlations that help in establishing, as a first approximation, the machines characteristic parameters also with reference to the different types of agitators. Hence, for the impeller speed, Njs , necessary to satisfy the just-suspended condition for solid particles in the vessel, AZwieterings criterionB w15x is usually adopted, for which the author prefers the following expression: ND 2
0.1

Reynolds number

/
n
sk

N 2D rl g Dr

0.45

/ /
d

0.2

Froudes number

/
D

B 0.13

1.

where: N s rotational frequency of the impeller, D s impeller diameter m., n s viscosity Pa s m., r l s liquid density kg my3 ., g s acceleration of gravity m sy2 ., D r s density difference, gasliquid kg my3 ., d s particle diameter m., k s constant see text., a s constant see text., T s tank diameter, B s distance from impeller midplane to tank bottom, m. This equation highlights the relationship existing between Reynolds number, Froude number, the ratios of the impeller diameter to the particle diameter

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and of the tank diameter to the impeller diamater and the percentage ratio B, between liquid and solid masses in the suspension w16x. Since all the quantities in brackets only refer to the physical system, they can be symbolized by a single dimensional settling parameter Y , while the impeller is characterized by its dimensionless value S w16x, where S s k TrD . a and k and a depend on impeller type and relative blade height. Finally, the criterion can be written: Njs s SYDy0 .85

Table 1 Impeller speed calculated using Zwieterings and Nienows correlations Rushton Zwieterings correlation turbine rad sy1 m sy 1 rpm diameter m 1.00 0.67 2.59 3.65 2.59 2.44 Nienows correlation rad sy 1 m sy 1 rpm 4.45 6.68 42.50 95.60

25.00 4.45 35.00 10.00

2.

When designing the Porto Torres reactors the following correlation, proposed by Nienow w17x, was used: NCD s 4 D2
0.5 0.25 QG T

3.

e s volume fraction of liquid in the suspension volume concentration of solids., dimensionless, VG s air superficial velocity based on tank cross-section gas flowrate divided by cross-sectional area of the tank my1 .. For a six flat-blade Rushton disc impeller, Neale and Pinches w21x report the following application of vant Riets equation:
k L a s 0.0069

where: NCD s rotational frequency of the impeller at which the gas is just dispersed throughout the vessel. QG s volumetric gas flowrate m3 sy 1 ., for crosschecking the results obtained with Zwieterings criterion. It was no surprise that the values obtained were quite different, as Table 1 shows. The optimum speed, measured over one years pilot plant operation, was 5.65 rad sy1 54 rpm., 34% higher than Zwieterings correlation and 43% lower than w18x. For impeller power prediction either Mills et als. correlation w19x: PT V s

/
V

PG

0.52

VG0.24

6.

where: PG s agitation shaft power gassed., kW, and for the BX04 Impeller: k L a s 0.0084

/
V

PG

0.79

VG0.58

7.

kL a 0.10 y 0.0018 e

1 .4925

1 VG0.4627

4.

or vant Riets correlation w20x: P s V

It goes without saying that adequate experimentation is required. Both correlations require the tank volume and the air superficial velocity to be known. The useful tank volume is calculated by multiplying the suspension volumetric flow rate, VP , by the residence time, uD p ; the latter, in turn, is derived by setting the desired percent sulphide removal, D p, and introducing this condition into the equation being K c s kinetic coefficient for pyrite solubilization, hy1 .:

k L a.

1.4286

1 VG0.2857

0.0001

5.

uD p s

ln 1 y D p . yK c

8.

can be used, where: P T s total power input agitator power q bubble expansion power, kW., P s power to produce suspension to height H kW.. V s liquid volume plus particle volume below airliquid interface m3 ., k L s overall liquid phase mass transfer coefficient m sy1 ., a s interfacial area m2 my 3 .,

which was derived for pyrite w22x, under the assumption that its oxidation reaction is first order, by integrating the following equation: d w FeS 2 x dt s yK c w FeS 2 x

9.

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The kinetic coefficient, K c , is obtained empirically, usually from bench scale tests carried out either in agitated Erlenmeyer flasks or in STRs whose carefully optimized performance is taken as the absolute optimum for pyrite oxidation kinetics. It is reasonable to assume that it is precisely this passage that is the pitfall behind the design procedure; in effect, this assumption equates to stating that the pyrite oxidation kinetics in the STRs are the best achievable and are intrinsic of the biooxidation process. Thus, the K c adopted for the Porto Torres plant bioreactors was 1.2 = 10y2 hy 1 w22x, but the value calculated from the results of one years plant operation turned out to be considerably higher, 1.53 = 10y2 hy 1 w23x. Tests carried out using bioreactors of new concept operated under the same conditions as the STRs w24x yielded much higher K c . In effect, the dependence of K c on several factors is well documented though never explicitly stated. Of these, solids concentration plays a major role in STRs and in Pachuca tanks. The limit of about 20% solids concentration for metals sulphides bioleaching in STRs was experimentally ascertained by several researchers w25x as long as 30 years ago and today has become an accepted rule for commercial plants, as shown by Table 2. This limitation is the major drawback of STRs, since it affects both investment costs size of the machinery. and operating costs power and maintenance..

4.2. The Pachuca tank Several researchers w4,2629x have developed correlations for predicting power requirements and oxygen mass transfer coefficients of this type of reactor. A great deal of work has been done by the Delft University school. After Bos et al. w30x, for large Pachucas the following simple correlation holds: k L a s 0.6 VG

10 .

whereas Boon et al. w29x proposed the following empirical correlation: k L a s 2.29 = 10y 2

QG V

0.66

/
0.66

11 .

where: k L a s volumetric mass transfer in a slurry, sy1 , that, combined with Lamonts power dissipation law w26x yields: k L a s 2.29 = 10
y2

/
V 1
0.66

= p 0 ln

p 0 q r f gH p0

12 .

where: p 0 s atmospheric air pressure Pa., r f s fluid phase pressure Pa., H s suspension interface height above vessel bottom m..

Table 2 Data of commercial and semicommercial biohydrometallurgical plants Name of mine or plant Feed to the plant GAP GAP GAPyP GAP GAP GAPyP Sulphur assay % 22.6 18 24.9 2024 2030 11.4 Reactor type STR STR STR STR STR STR Reactor size m3 . 90 160 1 = 580 9 = 450 6 = 480 3 modules 6 = 900 per module Daily throughput tonnes. 35 40 150 158 120 720 Solids concentration %. 20 20 20 18 20 Residence time h. 96 24 120 91.2 96 Reference

Fairview South Africa. Harbour Lights Australia. Sao Bento Brazil. Wiluna Western Australia. Youanmi Western Australia. Sansu Ashanti, Ghana.

w3,37x w3,37x w37,38x w39x w40,41x w3,42,43x

GAP s gold-bearing arsenopyriterpyrite flotation concentrate; GAPyP s gold-bearing arsenopyriterpyrrhotite and pyrite flotation concentrate.

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According to Meester Meester, pers. written commun. 1992., an equation describing the correlation among the variables influencing mixing can be derived if it is assumed that mixing takes place in two steps, and on this there is general consensus. On a large scale, the flow of the reactor contents produces mixing by convection, while further mixing takes place by diffusion on smaller scale. The state of mixing that thus is attained by turbulent flow is determined by the size of the smallest eddies in the flow pattern, for which the following definition is proposed by Hinze w31x:
1

le s
2 rm

hf3

/
V

13 .

where: l e s smallest turbulent eddy size m., hf s intrinsic fluid phase viscosity Pa s., rm s slurry density below slurry-liquid interface kg my3 .. For suspensions, Zwieterings correlation is valid also for Pachucas, within the above mentioned limits. The bioleaching performance of Pachuca tanks also rapidly decreases when the oxidizable solids concentration rises beyond 20% w25x with the same implications, as far as metal sulphide solubilization rate constant is concerned, already discussed for the STRs. 4.3. The importance of solids concentration All endeavours to employ STRs and Pachuca tanks for bioleaching metal sulphide suspensions with oxidizable solids concentrations higher than about 20% have so far failed. The reasons for this limitation have been the subject of much speculation, extensively discussed in earlier reviews w4,7,32,34x. The problem has been approached from the strictly abiotic viewpoint in chemical engineering journals with several interesting suggestions. However, only recently has some light finally begun to be shed on these intriguing issues thanks to the contributions of South African and Australian researchers w35,36x. Evidence was provided by Ragusa that mechanical and brutal detachment of microorganisms from the mineral surfaces to which they adhere during

bioleachingsuch as that produced by shear stresses acting within the suspensioncauses irreversible damage to microbial cells that, despite still being viable, lose their ability to adhere and oxidize the minerals. Moreover, Hansford and Bailey w32,33,36x produced evidence that the determining factor in bioleaching is the proportion of oxidizable solids, i.e. the oxygen-consuming solid fraction in the suspension, not simply the solids concentration. Those solids that are inert to oxidation only slightly affect the process. Under the above assumptions, the presumed threshold value of about 20% solids concentration would mean, quite simply, that the oxygen mass transfer coefficient of the STRs and Pachucas currently used in biohydrometallurgy does not provide, in the best operating conditions, enough oxygen for oxidizing larger amounts of metal sulphides. Any attempt to enhance reactor performance by increasing aeration inevitably results in increased agitation and greater shear stresses within the suspension and possibly waste of injected air due to partial flooding. Greater damage to microorganisms and insufficient oxygen mass transfer are probably the reasons behind what may be defined the A20% threshold solids concentrationB. The experimental results of bench scale and pilot plant operation for coal biodepyritization support these conclusions. At Deutsche Montan Technologie DMT. in Essen, Germany, and at Delft University The Netherlands. bench scale tests were carried with Pachuca tanks that were successfully operated up to 40% coal assaying 2% pyritic sulphur. w44,45x; the 8-m3 STRs of the Porto Torres pilot plant performed very well with a 40% solids suspension of the same coal w25x. In this perspective, the difficulties in developing a satisfactory conventional bioreactor design are obvious and probably unsurmountable.

5. The new developments in biohydrometallurgical reactor design The growing awareness of the inadequacy of STRs and of ALRs to cope with the problems inherent in biohydrometallurgical processing owing to the conflicting requirements to enhance agitation, for Oxy-

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gen Transfer Rate OTR. increase, and the one hand, and of a quiescent environment with negligible shear stresses on the other, has prompted the search for new types of reactors where these conditions are fulfilled to as great an extent as possible. Following, these new developments will be reviewed. It is fair to mention first the contributions by Andrews et al. w46,47x whowith a view to developing a reactor suitable for coal biodesulphurization already in the late 1980s focussed their attention on the features that this new reactor should have had. Based on the consideration that the relatively low value of coal called for low biodesulphurization plant investment and operating costs, Andrews found, when investigating the kinetics of pyrite bioleaching, that small reactor volumes, high solids concentrations of the suspensions and the largest possible active microbial populations were the objectives to be pursued. As for microbial populations, Andrews committed himself to giving the size of the most suitable microbial population: 10 18 bacteriarcm3! A figure that then would have probably been considered almost science fiction. 5.1. The aerated trough bioreactor [48] On these grounds, Andrews and his research team developed what they called A aerated trough bioreactor B. The device basically consists of a long rectan-

gular tank with V-shaped bottom, along which a perforated pipe runs that acts as an air sparger Fig. 2.. The reactor is structurally identical to the Callow-type pneumatic flotation cell w49x. Its most significant feature resides in the fact that it operates in a manner very similar to the plug flow reactor, hence complying with the kinetics of pyrite bioleaching w9x. As far as aeration is concerned, it is doubtful that there was any improvement in OTR, since the drawbacks of pneumatic reactors, like the Pachucas, do not seem to have been overcome. In effect, the k L a in water was 0.070 sy1 , whereas it decreased to 0.012 sy1 in a 45% solids concentration pulp, i.e. by about one order of magnitude wAndrews, 1990x: this suggests that aeration was unsatisfactory. 5.2. The Low Energy Bioreactor [50] Almost contemporaneously to Andrews aerated trough a research team of the CRA Company, active in Australia, made a successful attempt to solve the problem of maximizing OTR without inducing excessively large shear stresses in the suspension. The device they developed, called a A Low Energy Bioreactor B, basically consists of three components Fig. 3.:i. a tank, where bioleaching is carried out; the Aoff-the-bottomB condition for the solids being satisfied by an agitator, operating inside of a draft tube, most likely for reducing the shear stresses; ii. an aeration device where the pulp is very energeti-

Fig. 2. Aerated trough bioreactor w48x.

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Fig. 3. Low energy bioreactor, after w50x.

cally aerated by means of a Venturi pipe; iii. a pump for pulp recirculation. This device represents a major step forward in the development of a tailor-made bioreactor for biohydrometallurgical processes; certainly as far as power requirements are concerned, as emphasized by the authors. The resort to separate aeration is also a significant feature, insofar as it permits the pulp to be aerated as intensively as needed. However, the suspension is subjected to violent turbulence and shear during its residence inside the aerator. Further doubts remain as to the shear stresses i. generated within the pulp by the impeller, ii. produced inside of the annulus where, similarly to what happens in the Pachuca tank, the pulp flows upwards and iii. induced in the pulp by the pump, by means of which the pulp is repeatedly circulated. It was not possible to find data concerning the k L a of this device in the literature. It is a well known fact that air flowrate alone is not sufficient, insofar as it does not provide a measure of the air actually dissolved into the pulp, as demonstrated

experimentally by Andrews and Quintana w48x. Neither data concerning cell growth, cell numbers and residence times could be found. Furthermore, the inventors claim that their machine was developed for processing low-grade ores such as run-of-mine. obtaining iron leaching rates from pyrite of about 6 g dmy3 dayy1 . However, this performance is not exceptional since in the STRs of the Porto Torres pilot plant the research team of the CEC project observed iron leaching rates from pyrite in coal, hence comparable to a low-grade run-of-mine ore, as high as 9.2 g dmy3 dayy1 .This result suggests that the objective of achieving an atmospheric oxygen mass transfer coefficient high enough to promote a drastic increase in microbial population and finally in pyrite solubiliztion kinetics has not been attained. 5.3. The falling laminar liquid film principle It has long been recognized w51x that mass transfer across gasliquid free surfaces plays a very important role in several natural and technological processes, ranging from oxygen supply and CO 2 re-

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moval from animal cells and cultures to aeration of the culture media of shaken flasks or STRs, wastewater treatment and industrial microbial processes, like winevinegar manufacture and respiration of aerobic life occurring near the sea or lake surfaces w4,52x. A free-falling laminar liquid film poured into a pool of the same liquid can be designed in such a way as to cause very slight shear stresses in its bulk or in the liquid layers located near to the surface of the pool. Therefore, it is only natural to consider investigating the potentials of a three-phase biohydrometallurgical reactor designed in such a way as to utilize, for atmospheric oxygen transfer, the properties of falling laminar liquid films. Based on this concept two independent research teams, operating at the Universities of Cagliari Italy. and Delft The Netherlands. endeavoured to develop this new type of bioreactor. 5.4. The Delft Inclined Plate (DIP) Bioreactor [53] This device is schematically shown in Fig. 4. It consists of a main tank T., containing the slurry S.:

the solids are kept in suspension by an inclined agitator A.; a pumping device P., draws the suspension from the main tank and conveys it, through a distributing system, to the head tanks D., that feed the inclined plates S p .; the suspension flows down these slopes cataracting into the main tank. According to the inventors, atmospheric oxygen transfer is produced by the sheets of suspension plunging into the liquid surface of the main tank and entraining air bubbles. The magnitude of oxygen transfer is adjusted by setting the length and slope of the inclined plates and of the free-fall height as well as of the suspension flow rate. The device has only been tested with plain water and the authors claim lower power requirements and higher k L as than STRs and Pachucas. The highest k L a value in water is reported to be 0.0384 sy1 , i.e. 138.24 hy1 , hence very close to the k L a of the STR Fig. 5.. The most attractive feature of the device seems to be the low power demand and, possibly, the mild agitation required for mixing. However, the presence of the agitator, A, and of the pumping

Fig. 4. Delft Inclined Plate Bioreactor. A s agitator; D s head tanks of inclined plates; S p s inclined plates for slurry cascading; S s slurry; T s main tank; P s pumping device.

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Fig. 5. Mass transfer coefficients for atmospheric oxygen in water for the most common bioreactors. 1. plunging jet reactor w56x; 2. deep jet fermenter w56x; 3. mechanically stirred tank w56x; 4. axial flow turbines w56x; 5. multiple Rushton turbines w56x; 6. single Rushton turbine w56x; 7. simple bubble reactor w56x; 8. deep shaft areator w56x; 9. air-lift Pachuca-type reactor w28x; 10. vortex agitation reactor w56x; 11. Biorotor w55x; 12. low energy bioreactor w50x; 13. aerated trough bioreactor w47x; 14. Delft Inclined Plate Bioreactor w53x; 15. Biorotor w57x; 16. aerated trough bioreactor measured in a 45% solids suspension w47x..

device still appears to involve some shear stresses within the suspension, thus partially offsetting the advantage of less violent aeration. No testing on mineral suspensions has been carried out so far with the DIP, hence it is not possible to properly assess its potential for biohydrometallurgy. As far as the mode of oxygen transfer is concerned, the contribution of the contact of the relatively large surface area of the cataracting water sheet with the atmosphere should not be neglected, although very little is known on this topic w51,54x, and it warrants further investigation. 5.5. The reoling drum bioreactor A Biorotor B [55] From the very first endeavours to transfer biohydrometallurgy from bench to pilot to commercial

scale the Achilles heel of this new, promising biotechnology was the inadequacy of the reactors used w7x. Previous experiences were very helpful: the sinkand-float drums were very effective for gravity separation of ores their operation being very quiet and smooth. The only drawback was that, in certain conditions, the entrainment of air caused by part of the suspension plunging into the pool that formed in the lower half of the drum produced a certain instability. In the sink-and-float drum, this was an undesirable effect: the reverse would have been true had it been intended to mix the air with the suspension. The first prototype of the revolving drum bioreactor was developed in 1991, but it was only in 1993 that the final version of what was baptized ABiorotorB was thoroughly tested, first with plain water and finally with pure pyrite.

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An isometric view of the device is shown in Fig. 6: it has been exhaustively described in earlier papers, which the interested reader should consult for more details. In short, the reactor consists of a cylindrical barrel whose inner wall is fitted with regularly spaced lifters L.. Each lifter forms, with the inner wall of the barrel, a sort of tray where the suspension collects. The suspension and the air plus carbon dioxide mixture are conveyed through a pipe T. fitted into one front head M. of the barrel the Afeed headB .; a pipe fitted into the opposite head is the exhaust outlet. As the barrel revolves on its rollers R., the suspension is lifted upwards and when the tray reaches the top position it is discharged as a thin cataracting film with length equal to height of the cylindrical barrel. Oxygen mass transfer most occurs during the cataracting and when the free falling film plunges into the pool of suspension in the lower part of the barrel. This mode of operation ensures the satisfaction of all the prerequisites listed above for the ideal biohydrometallurgical reactor: i. mixing is complete with-

out any Adead volumesB; ii. the only shear stresses induced into the suspension are limited to the relative motion of the plunging film with respect to the suspension in the pool: for a 2-m diameter barrel, this relative speed is lower than 2 gHf s '2 P 9.81 P 1.4 s 5.24 m sy1 the free-fall height, Hf , being 0.7D . and the suspension drops into the upper few millimetres of the top layer, iii. a value of k L a of at least one order of magnitude larger than that of an optimized STR Fig. 5.. The most interesting feature of this bioreactor is, however, that the OTR actually matches the k L a : i.e. the oxygen is made available to the microflora that can attain much higher growth kinetics than those currently reported in the literature. Tests carried out with a 30% solids suspension, the solids being museum-grade pyrite, yielded solubilization rates as high as about 600 g my3 hy1 . This means that the rate constant is at least one order of magnitude higher than the value considered until now as the maximum obtainable. Hence, the Biorotor exploits, at a very high level, the potentials of the microflora for enhancing pyrite solubilization.

Fig. 6. Isometric view of Biorotor.

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Fig. 7. Plot of k L a vs. rotation speed for Biorotor w55x.

Fig. 7 gives the values of k L a corresponding to the range of rotation speeds considered as most suitable for biohydrometallurgical purposes w55x. It seems rather trivial, but some remarks that have appeared in the literature seem to justify pointing out that at rotation speeds higher than v s 0.5 gD . 0.5 Acritical speedB, corresponding to centrifugation of the suspension. the machine does not work. For the Biorotor prototype, which has a diameter of 0.3 m, this critical speed is 7.62 rad sy1 corresponding to 72.8 rpm.. Investigations carried out on a refractory gold-bearing complex sulphides concentrate with a conceptually similar machine w57x confirmed the superior performance of Biorotor, although it was only operated at 0.16 rad sy1 . In effect, extrapolating the lower branch of the diagram of Fig. 7 yields the same values for k L a. 6. Conclusions The experience gained over more than 30 years of laboratory research and commercial operation clearly

points out the undeniable limitations of the reactors used so far for metal sulphide minerals bioleaching. These limitations are related to the intrinsic structure and mode of operation of these machines insufficient mass transfer coefficient, high shear stresses induced into the mineral suspensions, to mention just the most significant. as well as to poor accuracy of the design formulae. The new devices proposed over the last decade are a clear demonstration that the designers have achieved a full understanding of the specific features that should characterize the biohydrometallurgical reactors: namely, effective Oxygen Transfer Rate OTR., effective but mild mixing and, consequently, low retention times and low specific power requirements. The experience gained with the latest developments, the revolving drum bioreactor, has clearly demonstrated that with an efficient reactor microbial growth can also be optimized. Most of these encouraging results have, however, been obtained empirically: more theoretical research

230

G. Rossi r Hydrometallurgy 59 (2001) 217231 w15x T.N. Zwietering, Suspending of solid particles in liquid by agitators, Chemical Engineering Science 8 1958. 244253. w16x J.J. Frijlink, PhD Physical aspects of gassed suspension reactors, Thesis, University of Delft, 1989, 119 pp. w17x C.M. Chapman, A.W. Nienow, M. Cooke, J.C. Middleton, Particle-gasliquid mixing in stirred vessels. Part IV: Mass transfer and final conclusions, Chemical Engineering Research and Design 61 1. 1983. 182185. w18x G. Loi, A. Mura, P. Trois, G. Rossi, La biodepiritizzazione del carbon fossile. Limpianto pilota di Porto Torres, Memorie dellAssociazione Mineraria Sarda-Iglesias, Italia, 1994, pp. 2941. w19x D.B. Mills, R. Bar, D.J. Kirwan, Effects of solids on oxygen transfer in agitated three-phase systems, AIChe Journal 33 9. 1987. 15421549. w20x K. vant Riet, Review of measuring methods and results in gasliquid nonviscous mass transfer in stirred vessels, Industrial and Engineering Chemistry Process Design and Development 18 1979. 357364. w21x J.W. Neale, A. Pinches, Determination of gasliquid mass transfer and solids suspension parameters in mechanicallyagitated three-phase slurry reactors, Minerals Engineering 7 2r3. 1994. 389403. w22x N. Orsi, G. Rossi, P. Trois, P.D. Valenti, A. Zecchin, Coal biodesulfurization: design criteria of a pilot plant, Resources Conservation and Recycling 5 1991. 211230. w23x G. Loi, A. Mura, P. Trois, G. Rossi, The Porto Torres biodepyritization pilot plant: light and shade of one year operation, Fuel Processes and Technology 40 1994. 261 268. w24x G.S. Hansford, Recent developments in modeling the kinetics of bioleaching, in: D.E. Rawlings Ed.., Biomining, Springer, Berlin, 1997, pp. 153175. w25x G. Loi, A. Mura, P. Trois, G. Rossi, Bioreactor performance vs. solids concentration in coal biodepyritization, Fuel Processes Technology 40 1994. 251260. w26x A.G.W. Lamont, Air agitation and Pachuca tanks, Canadian Journal of Chemical Engineering 1958. 153160. w27x N.N. Clark, Predicting the circulation rate in Pachuca tanks with full height draft tubes, Transactions of the American Institute of Mining Engineers 276 1984. 226232. w28x G.G. Roy, R. Shekhar, Oxygen mass transfer in air-agitated Pachuca tanks, Section C: Mineral Processing and Extraction Metallurgy 105 1996. 921. w29x M. Boon, T.A. Meeder, J.J. Heijnen, K.Ch.A.M. Luyben, Influence of oxygen adsorption on the dynamic k L a measurement in three-phase slurry reactors, Biotechnology and Bioengineering 40 1992. 10971106. w30x P. Bos, T.F. Huber, K.Ch.A.M. Luyben, J.G. Kuenen, Feasibility of a Dutch process for microbial desulphurization of coal, Resources, Conservation and Recycling 1988. 279 291. w31x J.O. Hinze, Turbulence: An Introduction to its Mechanism and Theory, McGraw-Hill, New York, 1959, 586 pp. w32x G.S. Hansford, A.D. Bailey, Oxygen transfer limitation of bio-oxidation at high solids concentration, in: A.E. Torma, J.E. Wey, V.I. Lakshmanan Eds.., Biohydrometallurgical Technologies, vol. 1. 1993, pp. 469478.

is needed so as to develop reliable design and scaleup procedures based on sound theoretical foundations.

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