ADVANCES TECHNOLOGY,

IN SULFIDE

SMELTING

R & D, AND EDUCATION

Department

H. Y. Sohn of Metallurgical Engineering University of Utah Salt Lake City UT 84112-0114 and

V. Ramachandran ASARCO Technical Services Center Salt Lake City, Utah

Abstract The considerable progress made in the sulfide smelting technology since the first International Sulfide Symposium of 1983 is discussed. The new developments and innovations have largely been driven by the recognition of environmental concern as well as the need for increased productivity. The smelting technologies for various nonferrous metals are reviewed, with an emphasis on the industry trend towards larger plants and continuous processes. The tremendous advances made in process modeling and computer simulation to describe the complex smelting processes are also reviewed. The goal of these mathematical models is the quantitative description of the processes and the reactors that will provide a means for the control and optimization of smelting operations as well as the optimal design of the operating conditions and the reactors. Environmental issues remain a key consideration in the smelting industry. One of the most remarkable improvements made in the last fifteen years since the 1983 Sulfide Smelting Symposium is the rapid increase in the sulfur capture by nonferrous smelters. This and other related issues are briefly discussed. Finally, the challenges that the smelting industry faces as the new millenium approaches are discussed. The industry continues to face technical challenges to improve productivity and efficiency, while being responsive to ever-increasing public pressure for environmental protection. It also faces external challenges from factors that may cause the reduction of metal uses as a result of substitutions by other materials. Another serious challenge and dire consequence that the primary metals industry is expected to face is the serious diminution of university-educated manpower as well as basic-research output. To remain competitive and healthy, the industry should take up the void left by the complete disappearance, at least in the U.S., and the reduction in other nations, of the governmental support of higher education and basic research in the field of primary metals production. Sulfide Smelting 98: Current and Future Practices
Edited by J.A. Asteljoki and R.L. Stephens The Minerals, Metals &Materials Society, 1998

I I

I. INTRODUCTION The First TMS Sulfide Smelting Symposium was held fifteen years ago in San Francisco and memorialized a time of great change in our industry [Sohn et al., 1983a; 1983b]. This was the period when the need for process changes to address growing environmental and cost challenges was finally recognized on a worldwide basis. To be sure, years prior to this time many companies had arrived at the conclusion that major technical restructuring of our industry was necessary. There were still a large number, however, who believed that emission control, productivity gains, energy efficiency and hygiene were only political drivers and they were immune to these pressures because of favorable geographic or political factors. Many believed, and a few holdouts still do, that 90% sulfur capture in smelters was about as good as was needed. The subsequent fifteen years has brought many changes. Strict emission regulations have become the norm in most areas of the world, the result of increasing awareness of the long-range effects of pollution and growing concern about health effect of sulfur oxides and heavy metals on workers. In spite of these advances large smelting facilities with limited or even no emission control equipment continue to operate in Australia, Canada, Chile, the CIS countries and in Africa. In industrialized countries, many old-style copper smelters found they were too small to absorb the cost of modernization or too dependent on marginal concentrate resources to be profitable. The resulting list of closures is long. It seems likely that similar forces will act in less-developed countries over the next fifteen years and result in significant smelter closures, possibly even whole-scale restructuring of an industry.

Bath smelting processes including the Noranda process and the closely allied Caletones Matte Treatment (CMT) process have been widely adopted, primarily as While it is elements of expanded smelter capacity and mainly in Latin America. certainly a robust technology and well suited for incremental expansion, the technology has not yet been demonstrated to meet the highest levels of emission control. It is likely that the major expansions using this technology have been completed. In the future, new applications of the Noranda/CMT reactors will likely be in new smelters, particularly those in the small to medium range (100,000 to 200,000 tonnes of copper per year) and where favorable political or economic conditions allow a degree of tariff protection for a new industry. The new smelter in Thailand utilizing a CMT reactor is a good example. The IsaSmelt Process and the closely related Ausmelt (also Sirosmelt) process were both developed in the 1980s and based on pioneering work conducted by CSIRO in Australia [Mounsey and Robilliard, 19941. The process concept is based on a single vertical lance for oxidant and fuel injection, incorporating proprietary lance cooling technology. A sketch of an Ausmelt furnace is shown in Fig. 1. Wet filter cake feed, in some cases pelletized, is directly fed to the cylindrical, vertical smelting vessel. The first semi-commercial plant for copper was constructed at Mt. Isa in the mid-1980s. A lead smelting plant was also constructed at Mt. Isa at about the same time. The process was also adopted by Cyprus-Miami Copper to replace the electric reverberatory furnace. The electric furnace was retained for the phase separation step and must be the largest slag cleaning furnace in the world. Several smaller Isasmelt and Ausmelt furnaces have been proposed or constructed for copper, and recently the Sterlite smelter in India commenced operation using a small Isasmelt. The process appears to be a good option for smaller plants, particularly ones with a source of secondary feed which can easily be smelted in the reactor.
LANCE

II. II-l. Conner Smelting

SMELTING

TECHNOLOGY

UPDATE
DETAILS
UNtE
Has, I

Expansion of copper smelting capacity has occurred primarily through the incremental expansion of existing smelters. Most Outokumpu flash furnaces have been expanded to more than double their original capacity by application of higher levels of oxygen enrichment and improved equipment reliability. There are currently over forty Outokumpu flash smelting furnaces in operation producing about 40% of the worlds primary copper [Kojo and Hanniala, 19941. Into has continued to develop its flash smelting process, but no new Into flash furnaces have been licensed since the early 1980s. Since the 1983 meeting, new Outokumpu-type flash furnaces were installed at Chuquicamata in Chile (1985), BHP Magma (1988), Olympic Dam (1988) Disputada de 10s Condes Chagras (1995) and Kennecott (1995). The smelter at Kennecotts facility in Utah utilizes a large Outokumpu flash smelting furnace in conjunction with the Kennecott-Outokumpu Flash Converting process. This process was first announced in 1983 at this conference. The solidification of matte from the smelting furnace has proven to be an effective approach to maximize the inherent flexibility of the smelter by avoiding the problems of maintaining and regulating continuous metal flows. The solid matte allows high levels of oxygen enrichment, and with the well-proven furnace design basis from Outokumpu the process can be designed for a wide range of smelter capacities. After some initial teething problems, the smelter is operating at well above design rates. Environmental control is exceptional with emissions less than 3.5 kg/tonne of copper or 99.9+ % sulfur capture.

Figure

1. A sketch of an Ausmelt

furnace.

(Courtesy

of Ausmelt

Technology

Corp.)

Reverberatory and electric smelting processes for copper are still utilized in many areas of the world but are coming under severe environmental and cost pressure. In most advanced countries with high energy costs and restrictive environmental regulations these processes have been among the first to be replaced. Application of oxy-fuel burners to reverberatory furnaces, first developed in the 1970s in Chile and the former USSR, is still finding application. Mitsubishis MI process was the first modem continuous smelting and converting process. This pioneering process development began in the late 1960s but aside from the in-house use at Mitsubishis own smelter and the early 1980s application at Kidd Creek the process was not enthusiastically embraced. Recently, the process has been sold for expansion of the LG Metals smelter in Korea (essentially a green-field smelter) and for green-field smelters in Indonesia (Gresik) and India. The process is suitable for copper production of up to 200,000 tonnes per year of new metal. CONTOP, which stands for CONtinous smelting and TOP blowing, is a combination of a high-intensity smelting process in a cyclone, characterized by extremely fast reactions as a result of optimal kinetic conditions, and secondary treatment of the molten phases with a top-blown jet [Sauert et al., 19941. The process was developed by KHD Humboldt Wedag AG in 1979 for smelting copper concentrates. A one-ton-per-hour pilot plant was used to establish the operating parameters and develop design data for large-size plants. CONTOP was first used as an extension of an existing reverberatory furnace at Codelco in Chuquicamata, Chile with a cyclone capacity of 500 tpd. In contrast, the entire smelting operations at the ASARCO copper smelter at El Paso were modernized using the CONTOP technology. The process was retrofitted into an existing copper smelter to utilize the existing gas handling and acid plant systems. Solid feed is smelted at a rate of 1320 tpd in two water-cooled cyclones with technical-grade oxygen. Through the integrated slag conditioning step by top-blowing lances, a discardable slag with low copper (0.7-0.9% Cu) is achieved. The mechanical carryover of dust was 1.7% with the total dust amounting to 4.5 to 6.5%, depending on the amount of volatile species in the feed. Hot commissioning of the Asarco plant began in March 1993. Following the usual start-up problems, intended capacity was reached in a week or two with acceptable metallurgical results. However, corrosion damage in the cyclone, similar to that experienced at Chuquicamata, occurred within a month. After considerable investigation of causes for this failure, a final design of tank-type cyclone made of stainless steel was arrived at and has oeen in use since April 1994. These cyclones can handle the heat of smelting for the currently intended matte grade of 58 to 60% copper. At present, the El Paso smelter produces about 100,000 tpy of copper from concentrates plus an additional 22,000 tpy by the processing of scrap through converters. Since establishing steady operations from April 1994, the CONTOP process has resulted in an increase of sulfur capture to 98%, an increase of acid production by 88%, an increase in copper production by 22%, and a reduction in emissions by 90%. The Kennecott-Outokumpu Flash Converting process is one of the few new processes discussed during the 1983 Meeting to have been commercialized. Some of the more daring processes have failed to meet expectations and are no longer used even by the originators.

11-2. Nickel Smelting Nickel sulfide smelting remains a relatively secretive industry. The major producers, Into, Norilsk, Falconbridge, Outokumpu, Bamangwato Concession Ltd. (BCL at Selebi Phikwe, Botswana), and Western Mining Corp., all use some form of flash smelting with Peirce-Smith converting to produce a low-iron matte. Many nickel smelters still utilize electric furnaces, but major advances in autogenous flash smelting (Outokumpus Direct Oxygen Nickel (DON) process and Intos Bulk Flash Smelting) offer some marked advantages over more traditional routes. In some ways the nickel smelting industry has just begun to face the environmental and cost pressures that have been such a large factor in copper smelting for more than two decades. Sulfur capture in nickel smelting remains very low and with the high sulfur to nickel ratios in the feed concentrate and generally remote smelter locations emission control will be costly. The Vanukov foam-bath smelting process for both copper and nickel has been applied at Norilsk, Balkash, and Sredneuralsk smelters, but it has not been adopted outside the CIS countries. In Australia, Western Mining Corp. seriously considered the process but abandoned the development effort when it became clear that optimization of the existing Outokumpu-type flash furnace was more cost-effective.

11-3. Lead Smelting Lead smelting has retrenched under enormous environmental and hygiene pressures and a difficult market. The sinter plant-blast furnace process remains dominant. In the early 1980s the sinter plant blast furnace process accounted for about 85% of all lead smelted in the western world. Since then, there has been considerable pressure to adopt direct lead smelting processes to minimize emissions and lower lead levels in ambient air. However, the well-known dilemma in the direct smelting of lead concentrates is that a low-sulfur bullion and a low-lead slag are mutually exclusive under equilibrium conditions [Mackey and Tarassof, 19831. Direct lead smelting processes that have been investigated and/or installed in the last fifteen years are listed below: 1. Boliden Kaldo (TBRC) process - Bath Smelting

2. QSL - Bath Smelting 3. ISASMELT/Ausmelt/Sirosmelt 4. KIVCET 5. Outokumpu - Flash Smelting - Flash Smelting - Bath Smelting

Of these five processes, only the Outokumpu process [Nermes and Talonen, 19771 has not proceeded beyond the pilot-plant stage. Although the Boliden Kaldo process [Wyllie, 19781 was originally developed for treating lead concentrates, it has been processing only secondary materials in the recent past with small amounts of concentrates in the charge. Both ISASMELT [Mathew et al., 19901 and Ausmelt [Short et al., 19961 use the top entry Sirosmelt lance system. Two ISASMELT plants have been built so far - one at Mount Isa for treating lead concentrates and the other at Britannia Metals for processing
-._.7.._. ._._ ..__.._ _

lead sulfate paste from spent batteries. The plant at Mountt Isa is on standby due to a shortage of feed material, and no information is available abomt the possibility of starting the unit in the near future. Metallurgie Hoboken has installled an ISASMELT furnace for processing lead concentrates and are in the process of ccommissioning the unit. No information is available at the moment about the details of :startup. The Ausmelt technology for lead was reviewed in a recemt paper [Short et al., 19961. Two lead smelters, Metaleurop Weser Blei, Nordenham and Tsumeb Corporation, Ltd., Namibia, have replaced their sinter plant, blast furnace 1e:ad smelting with Ausmelt technology. Both plants treat a wide and varying range of feed materials in an environmentally improved atmosphere. Metaleurop is mow at full capacity after overcoming problems with its flux-flow boiler and is startinig to work at improving its refractory life. Tsumeb completed commissioning the plant amd is undergoing rebricking after its first campaign. They are also rebuilding the evaponative gas cooler [Ausmelt Tech. Corp., 19971. The main advantage with Ausmelt is thee ability to run oxidizing or reducing conditions in the same furnace to allow primary amd secondary lead materials to be smelted in a single unit. Floyd (19961 has summariized all the applications of Ausmelt technology to date. The paper also outlines possibilities for potential applications in various areas of metallurgy and waste treatmcent. Operating experience of the QSL process has been well1 documented by Queneau and Siegmund [1996]. Recent operating data of the QSL reacctors at Stolberg and Korea Zinc are summarized in review papers [Deininger et al., 19942; Peacey, 19961. The third QSL converter, built in China in 1985, was commissioned in 1995. Although no operating details are available, it is claimed to have given good met;allurgical results at design capacity (52,000 tpy bullion) [Queneau and Siegmund, 199f6]. The QSL process has undergone considerable changes since its startup in 1989 to) its equipment design and operating practice and now appears to be operating at desigm levels. The KIVCET technology for smelting of lead concemtrates, which continues to operate successfully in the former Soviet Union, was started urp in Portovesme, Sardinia, in 1987 and is the longest-running direct smelting plant to date. Details of the Portovesme plant are described in papers by Perillo et al. [ 199tO] and Sentimenti and Cois [1996]. Recent operating performance of the KIVCET furmace at Portovesme has also been summarized [Peacey, 19961. The same reference also clompares the KIVCET and the QSL processes, showing all the operating parameters. Cominco at Trail, British Columbia is in the process of commissioning a KIVCET furmace. Summing up, there are now two proven direct lead smrelting processes to choose from, and ISASMELT/Ausmelt may become the third in the mear future [Peacey, 19961. Ausmelt has operated two units at Metaleurop and Tsumeb Corporation in Namibia for about a year. Its performance for the long haul will be wattched with interest. All of these processes are cleaner and more efficient than the sinter-plant blast furnace. The new lead smelting processes have a much higher capacity for secondaries (up to 25% of the charge) than the sinter blast furnace - a major advantage with increased levels of lead recycling.

11-4. Zinc Zinc pyrometallurgy is certainly on the wane. Zinc hydrometallurgy is simply too efficient and produces a high-grade product that cannot be matched by a simple smelting process. With the exception of a few specialized processes such as ISP and some zinc retort processes, the majority of production has been replaced by pressure oxidation or roast-leach-electrowinning plants. The initial optimism for a direct zinc sulfide smelting process has not materialized into a commercially viable process, but recently it was announced [Amer. Metal Market, 19971 that Zinc Corporation will construct a plant for zinc metal production in Peru, based on a process initially developed by Warner and coworkers [Warner et al., 19941. the chemistry involved in this process is shown in Table 1.

Table

1. Reactions

in the proposed

direct zinc smelting

process

a) ZnS + 2 Cu = Cu,S + Zn b) Cu,S + 0, = 2 Cu + SO, c) Overall Direct Smelting Reaction

ZnS + 0, = Zn + SO,

11-5. Platinum

Group Metals

which typically contain Smelting of platinum group metal (PGM) concentrates, nickel, is growing with several mini-smelters now in operation in addition to the older and larger (relatively speaking) PGM smelters in the Republic of South Africa. The Stillwater Smelter in Montana utilizes electric furnace smelting followed by matte granulation and TBRC converting to produce a high-value nickel-PGM matte [Matousek et al., 19891. The technology is innovative and the results impressive.

11-6. Other Metals Sulfide smelting processes for other metals has always been of minor interest. A direct molybdenum sulfide smelting process to produce high-grade molybdenum trioxide has not been commercialized, and further work is believed to have been stopped. The dominant metallurgy remains the direct roasting of high grade molybdenum sulfide concentrate. However, hydrometallurgical processes have been investigated to treat lowgrade concentrates, especially those containing rhenium [Daugherty et al., 19731.

11-7. Fundamentals

of Sulfide Smelting

The fundamental understanding of smelting was well represented during the 1983 Conference [Sohn et al., 1983a]. Pioneering work by Kellogg, Rosenqvist, Yazawa, Schuhmann, Themelis, Nagamori, and Jorgensen, to name a few, has now been expanded. The tools for extending the theoretical sulfide smelting fundamentals have become much 9

more effective. Recent work on modeling the flash smelting reactions including coupled computational fluid dynamics have been a significant factor in optimizing Outokumpu flash furnaces including the Kennecott-Outokumpu Flash Converting. Similar work has been carried out for the Mitsubishi MI Process and for Intos various nickel-copper converting-refining processes. Even the nearly century old Peirce-Smith converter has been the subject of considerable modeling and fundamental process investigation but the long-term value to operating companies has been debatable in the face of rising environmental costs. Extensive thermodynamic data bases with sophisticated physical chemistry modeling, supported by continuing fundamental studies of metal-sulfide-oxide systems, have extended the understanding of sulfide smelting. Investigation of minor metal behavior has also advanced significantly. Some of the important advances made in the areas of the fundamental principles and process modeling will be discussed in greater detail later in this paper. Compared with other industries, primary metals industry including nonferrous smelting industry, with a few exceptions, have for long lagged behind in carrying out or supporting R&D. With modem smelting plants becoming larger and processes more continuous, even modest incremental improvements now mean significant advantages. It is thus increasingly important for the industry to renew its support of R&D. Especially in the face of strong competition, the industry is in danger of completely losing even the small remnant of academic discipline in which new young metallurgical engineers are taught and trained on the subject. Already, we see very few, if any, new faculty members coming into academia that intend to make a career of teaching and carrying out research on pyrometallurgy. On whom is the industry going to rely to provide manpower to operate the plants and to perform the technical improvements and developments? While recognizing the valuable work of the pioneers mentioned above, it would be worthwhile to ponder this question.

ous deportment of minor metals, and low first-pass copper recovery. Continuous singlestage processing remains elusive and impractical for all but a few very high-grade concentrates. Outokumpu has supplied two direct copper production flash furnaces treating low-iron concentrates. The first of these was constructed in 1978 by KGHM Polski Meidz in Poland. The second was constructed in 1988 by Western Mining Corp. for their Olympic Dam Operations mine in South Australia. Olympic Dam is currently constructing a much larger direct blister flash furnace to accommodate a major production expansion at the mine. Noranda operated a continuous single-stage smelting and converting process in the 197Os, the original Noranda Process, but abandoned that approach and utilized the Noranda vessel as a matte producer. The QS coppermaking process, based on which the QSL leadmaking process was developed, was invented by Queneau and Schuhmann [1974] for producing copper directly from concentrates in a single vessel. Desired oxygen activity and temperature gradients are maintained in the reactor by the countercurrent flow of matte and slag phases through a series of bubble plumes formed by bottom gas injection [Queneau, 19931. A sketch of the process concept is shown in Fig. 2. Although it has many fundamental and technical merits, the QS coppermaking process has not yet seen commercialization.

III.

ADVANCES

TOWARD

CONTINUOUS

PROCESSES
0, + ShieldGas Coal+CmkrGas+02 + ShieldGas

Continuous matte smelting processes have been available for many years, some having quite high capacity and productivity. The conversion of matte to copper, however, has been almost totally dominated by the Peirce-Smith converter, which was developed some hundred years ago, and a few variants such as the Hoboken Converter. The inherent problems of multiple Peirce-Smith converters with their high gas volumes and difficult emission control problems have led to much creative thinking to eliminate this century-old process. Two approaches have emerged in this regard. One is the combining of the two steps into a single-step smelting process to produce the metal directly from the concentrate. The other is to develop a continuous converting process to replace the Peirce-Smith converter.

Figure 2. A schematic diagram of direct coppermaking reactor. (Adapted from Queneau [ 19931.).

QS

111-2. Continuous

Converting

III-l.

Sinple-Ster,

A single-step smelting and converting process poses many difficulties caused by the need to deal with managing the high heat release from the complete oxidation of sulfur and iron in copper concentrates, difficult slag with high magnetite content, disadvantage__ .10

Continuous converting has been studied extensively for years with many attempts to provide a controlled flow of molten matte to a continuous converting reactor. The practical limitations in transporting molten matte and integrating a converting process Recent information about the with the matte smelting step have stymied success. volatilization of toxic heavy metals such as cadmium, lead, and arsenic from molten matte may provide the additional impetus to better control open ladle transfer of molten matte or eliminate the practice. At the 1983 International Sulfide Smelting Symposium, Kennecott announced the development of their Solid Matte Oxygen Converting (SMOC) process, which overcame
ll_ _ _ .._

the limitations inherent in handling molten matte [Richards et al., 19831. This process is based on solidifying the molten matte from the smelting step and feeding this solid matte to an oxygen-fed converting furnace. This de-coupling offered great flexibility in the practical design of a smelter and provided a ready way to accurately control the feeding rate of matte and hence the chemistry of the converter. The thermal burden imposed by re-melting the matte in an autogenous process proved to be a significant advantage. By using high levels of oxygen enrichment, the off-gas from the converter is very low in volume, with gas strength in the range of 35% to 45% sulfur dioxide. The concept of solidifying the matte and re-smelting it to effect converting was unexpected and unusual, and there was initially great skepticism about the process concept. The process was developed in the mid-1980s in cooperation with Outokumpu and renamed the Kennecott-Outokumpu Flash Converting Process. While other reactor designs were envisioned in the original SMOC patent, the selection of an Outokumpu-type flash furnace reflected confidence in that furnace technology. In 1992 Kennecott announced that it would expend $880 million to construct a new smelter in Utah based on Outokumpu flash smelting and Kennecott-Outokumpu flash converting technologies [George et al., 199.51. That smelter was brought into commercial operation in June 1995 and is now operating well in excess of its original design capacity. Emissions are highly controlled with sulfur capture in excess of 99.9%, equivalent to 3 kg of SO, per tonne of copper, the lowest emission rate in the world. The primary advantages of the Kennecott-Outokumpu Flash Converting process are the use of well-proven Outokumpu technology; the de-coupling of the smelting and converting steps, which allows great flexibility; the high capacity of the converting furnace, which matches high output Outokumpu smelting furnaces, and the production of very small volumes of high-strength process gas, which minimizes the cost for emission control. Since 1983, several other continuous and semi-continuous converting technologies have been proposed and implemented. Into has developed several adaptations of the Peirce-Smith converter to effect continuous conversion of a high-grade matte concentrate derived from their nickel matte separation process known as MK concentrate. The initial design utilized flash gun or burners installed in a tuyere-less converter. High dusting rates and poor chemistry control made this a less-than-ideal process. Next, Into tried tuyere injection of a dried MK concentrate, but reportedly tuyere wear was unacceptable. Most recently they have added porous gas-sparging plugs to the vessel and top jetting of the oxygen to achieve reasonably high oxygen mass transfer. The MK concentrate is fed through openings in top of the furnace shell through lances or chutes where it is mixed into the bath and converted. Noranda Smelting and process. Matte be periodically has also developed an adaptation of their original Noranda Continuous Converting process for processing liquid matte in a semi-continuous will be added to a side-blown reactor and converted to copper which will tapped.

matte from the holding furnace. The anode furnaces will also be relocated to a point near to the C furnace to handle the continuous flow of blister copper. The smelter is small by world standards, with only 120,000 tonnes per year production.

IV. ADVANCES

IN R & D

Until about twenty years ago, most pyrometallurgical processes were carried out at or close to equilibrium conditions due to the high process temperature and the intermittent nature of most systems. As mentioned earlier, the newer processes must be of higher productivity and thus higher intensity which does not allow time for equilibrium. Therefore, a large number of reports on the rate processes, both chemical kinetics and transport phenomena, together with those on the measurement of transport properties, related to pyrometallurgical reactions started to appear in the literature about twenty years ago. The early investigations on pyrometallurgical rate processes mainly dealt with gas-solid reaction rates, which were systematically summarized in monographs coauthored by one of the authors [Szekely et al., 19761. Since these monographs were published, much more progress has been made on the subject [Sohn, 1997a]. In the meantime, the rate processes involving molten phases were also investigated, although to a much lesser extent. This is because they are almost always controlled by mass transfer process, with equilibrium at the interface. The list of individual systems investigated can be found in the annual reviews appearing in JOM [Sohn, 1976-1992; Sohn and Cho, 1993-19971. A very significant development in the last decade has been in the field of mathematical process modeling. Mathematical process modeling has become necessary because pyrometallurgical processes have become continuous and larger in scale with greatly increased throughput rates. Therefore, even a small increase in the efficiency and/or yield now means a much greater profit than before, Thus, optimization and control have become much more important for the newer processes. Simultaneously, large and fast computers have become available to enable us to solve the often extremely Some of the notable examples of these efforts have complicated governing equations. been in the following areas: In sulfide smelting: 1. 2. 3. 4. Flash smelting QSL-type and converting reactors equilibrium behavior areas: models of sulfide minerals

channel

Thermodynamic Minor-element

modeling

In other nonferrous 5.

Mitsubishi has also been active in promoting their C (converting) furnace technology for liquid matte feed. The Southern Copper smelter in Port Kembla, Australia is now owned by Furakawa. The smelter includes a small Noranda reactor and PS type converters. Furakawa will modify the smelter by elevating one of the converting vessels to a point 11 meters above the converter aisle and installing a vessel-weighing system. Molten matte will be charged to this holding furnace by overhead crane and ladle. A Mitsubishi c furnace will be installed and fed by controlled pouring of molten __ l-7

Fluidized-bed chlorination process [Zhou and Sohn, 1996; Youn and Park, 1989; Rhee and Sohn, 19901 Multihearth Hall-Heroult roasters [Saha Roy et al., 1992; Gupta et al., 19891 reduction cell [Wahnsiedler, 19871

6. 7.

aluminum mathematical

A well-constructed

model based as much as possible on first principles 13_ _ _ .._

provides not only a fundamental basis for the design and optimization of a complex process, but also a means of controlling the process as well as carrying out tests of the effects of process variables without having to resort to very costly tests in commercial or large-scale pilot plants. The use of mathematical modeling and computer simulations is expected to grow rapidly. In the following, we will briefly discuss selected mathematical simulations aimed at sulfide smelting processes. models and process

wlthln

turbulent

+
RADIATIVE . HEAT TRANSFER FLASH OF SMELTING MATHEMATICAL

d MODELING

IN LABORATORY FLASH FURNACE

IV-l.

Flash Smelting Computational

and Converting Fluid Dvnamic

Processes:
OTHER FLASH

PROCESS \ REACTION

PILOT-PLANT MEASUREMENTS

Modeling

Despite the important stature of flash smelting process in sulfide smelting, it has been relatively recently that realistic computer simulation of the process has been made. The main reasons for this are the complexity of the process and the fact that the computing capacity to solve the complicated equations describing such a process has become available only lately. Furthermore, a reliable method for computing turbulent fluid dynamics of a particle-laden gas jet has also been developed rather recently. Incorporating these developments, Hahn and Sohn [1990] constructed a 2-D mathematical model of the processes taking place in a flash furnace shaft. Their model contains the following features:

re and their interrelationships in the construction Fig ,w 3. Components the mathematical modeling of flash smelting process. (Adapted from Sohn [1991].)

of

well as a more detailed discussion of how the mathematical been presented elsewhere [Sohn, 19911.

model was constructed

has

(1) The

2-D turbulent fluid flow is described model that accounts for the dependency length on the local flow conditions. effect included. of the particles on turbulence

by the two-equation k-e of the turbulent mixing

(2) The

and thus fluid flow is

This model has been verified with the results of laboratory measurements in terms of particle distribution [Yasuda and Sohn, 199.51, gaseous concentrations, and sulfur contents in the particles [Hahn and Sohn, 19901 and minor-element volatilization [Seo and Sohn, 19911 and with those of independent industrial pilot-plant tests [Hahn and Sohn, 1990). Some verification results will be discussed below. The reader is referred to the original articles for more details.

(3) The

dispersion of particles due to the turbulent fluctuation of the velocity components is considered in describing the particle distribution. measured reaction kinetics of the feed particles are

Particle

Disnersion

(4) Separately
incorporated.

(5) Convective
included.

heat and mass transfer

between

the particles

and gas is

(6) Radiative

heat transfer processes are described by the four-flux model incorporating the absorption, emission, and anisotropic scattering phenomena.

In the only experimental investigation so far of the particle dispersion behavior in a flash smelting type system, Yasuda and Sohn [199.5] measured the particle number density distribution in a particle-laden gas jet. The measurements carried out at room temperature were made by taking photographs of the particles in flight which were analyzed by an image analysis technique. They then compared the measured results with the prediction of the above-mentioned mathematical model of flash smelting processes [Hahn and Sohn, 19901. The experiments were done using gas-particle injectors of single- and double-entry types. The effect of the diameter of a single-entry injector was studied using different injector diameters with the same air flow rate. Figure 4 shows the comparison of the projected particle number density plots for three different injector diameters. It should be noted that the projected number density is the number of particles per unit area of the photograph. Figure 4(a) shows the experimental plots, and 4(b) shows the predicted plots. The air flow rate was fixed at 0.028 Nm3/min, and the particle loading was 0.82 kgsolid/kg-air for all three conditions. The measured central particle number density for

Mathematical models are useful only if they can not only describe observed results but have the reasonable expectation for predicting results under varying operating conditions. In this respect, a model should be formulated based on a sound foundation and, as much as possible, on first principles. Considering the importance of this general requisite, the procedure in which the above-mentioned mathematical model for flash smelting processes was constructed, by combining the various components (which are separately well-understood) of the overall process, is illustrated in Fig. 3. This figure as
14

15

particle dispersion takes place after the jet is injected. It is desirable that the particles disperse widely and uniformly into the jet. To examine the effect of the inner tube diameter for the axial double-entry system, data for injectors with inner tubes of different outer diameter were compared. As a reference, the data for the single-entry l-inch (25.4 mm) diameter injector were also compared with that of the double-entry injectors. Figure 5 shows the comparison of the projected particle number density for different inner tube diameters. Figure 5(a) showed the experimental plots, and 5(b) shows the predicted plots. The air flow rates for the double-entry injectors were 0.014 Nm3/min for the primary and 0.084 Nm3/min for the secondary. The particle loading was 1.64 kgsolid/kg-air for the primary air and 0.23 kg-solid/kg-air for the total air. The air flow rate

Radial Position (m)

Radial Position (m)

Radial Position (m)

Figure 4. Effect of injector diameter on projected particle number density in a particle-laden gas jet from a single-entry injector (- 1 inch, ... l/4 inch, --- l/8 inch). (a) top: experimental. (b) bottom: predicted. (air flow rate = 0.028 Nm3/min; 150 mm below the jet entry) (Adapted from Yasuda and Sohn [1995].)

the l-inch injector is seen to be hyice as high as that of the other injectors. In the predicted results, the particle number density in the center of the jet decreases with decreasing injector diameter. The major disagreement is the width of the profile. This was explained as an artifact of the experimental configuration of the injector, rather than an inherent behavior of the jet [Yasuda and Sohn, 19951. This artifact becomes less significant when the injector tip diameter was increased to 1 inch. The agreement between the experimental and predicted results is satisfactory when the diameter of the injector is sufficiently large. For the axial double-entry system, the particles and primary air were supplied through the inner tube, while secondary air was introduced through the annulus between the inner and outer tubes. The geometry of the axial double-entry type injector is similar to that of the Venturi-type concentrate burner [Lilja and Makitalo, 19791 used for the flash-smelting furnace. Since the particles are injected separate from the process air, the

Radial Position (m)

Figure 5. Effect of inner tube diameter on projected particle number density in a particle-laden gas jet from a double-entry injector with l-in I.D. (- double entry with 7/8-inch O.D. inner tube, ... double entry with l/2-inch O.D. inner tube, --- single entry with l-inch injector). (a) top: experimental. (b) bottom: predicted

(150 mm below the jet entry; air flow rate = 0.014 Nm3/min for primary and 0.084 Nm3/min for secondary) (Adapted from Yasuda and Sohn [1995].)
17

16

for the single-entry injector was 0.084 Nm3/min. In the experimental results, the plot for the double-entry injector with the l/2-inch inner tube shows a narrow peak in the center of the jet, while the plot for the 7/8-inch inner tube is a wider peak. The plot for the single-entry injector has a shape between the plots for two double-entry injectors. The The predicted results are close peak heights of these three plots are almost identical. injector with representations of the experimental results. The plot for the double-entry the 7/8-inch inner tube indicates the widest and smoothest profile of the three plots. The plot for the l/2-inch inner tube shows a sharp peak in the center of the jet. The peak of the predicted plot for the l/2-inch inner tube is again narrower than that of the experimental plot, as observed in the case of single-entry injectors. The plot for the single-entry l-inch injector shows a similar profile to the plot for the double-entry Overall, the mathematical model adequately injector with the 7/8-inch inner tube. represents the particle dispersion phenomena in a turbulent gas jet.

velocity of 4 m/s while varying the solid feed rate accordingly. Reasonable agreement between the predicted results and the measured data was obtained, except near the furnace bottom. It is noteworthy that the model adequately predicts the ignition point of particles, which is important to properly predict the smelting process occurring in the flash furnace shaft. The deviation near the bottom of the furnace is due to the air leaking into the furnace through an opening at the bottom for the sample probe [Chaubal, 1986; Hahn and Sohn, 19901. The effect of oxygen concentration in the inlet gas is shown in Figure 7. The linear injection velocity of the gas was 4 m/s, and the target matte grade was kept the same at 70 pet in both cases by adjusting the solids feed rate. Although the deviation near the furnace bottom attributed to air infiltration is observed again, the overall agreement is satisfactory.

Flash Smelting

Reaction

Experimental work was carried out in a large laboratory flash furnace to measure the amount of sulfur remaining in the the centerline profiles of the SO? concentration, particles, and the gas temperature [Chaubal, 1986; Sohn et al., 19881. In this system, the gas and solid particles were uniformly mixed in a mixing chamber prior to being injected as a single stream. The burner was a straight cylinder of 2 cm diameter. The effects of oxygen content in the inlet stream and solids loading on the reaction of chalcopyrite concentrate were investigated. between model predictions and measurements Figure 6 shows the comparison obtained for target matte grades of 50 and 70 pet with 21 pet 0, and a fixed injection

025

05

075

10

125

Axial

Distance

from

Top (m)

Figure 7. Comparison of experimental and computed results for the variation of gas composition and the sulfur content in the particles along the centerline of a laboratory flash furnace. (experimental data + 21 pet O,, 0 30 pet 0, and target matte grade of 70 pet Cu vs. prediction --; For the two different oxygen concentration in the process gas, the gas injection rate was kept the same while the solids feed rate was adjusted to give the same target matte grade of 70 pet. Conditions for the experimental runs are given in Hahn and Sohn [1990], from which the figure is adapted.) Figure 8 shows a similar comparison between the model predictions and measurements obtained in an Outokumpu pilot plant having a single-entry burner [Hahn and Sohn, 19901. The top figure shows the SO, and O2 concentrations as functions of centerline axial distance from the burner, as well as the amount of oxygen used in the oxidation of metal contents. The second graph is for the case of preheating the feed gas. Considering the complexity of the process and the fact that the pilot-plant measurements were donecompletely independently from our computation, the agreement is remarkable. The bottom graph compares with temperature profiles for these two cases. Again, the agreement iS very good.

Axial

Distance

from Top (m)

and computed results for the variation of gas Figure 6. Comparison of experimental composition and the sulfur content in the particle along the centerline of a laboratory flash furnace. (experimental data + 70 pet Cu, x 50 pet Cu, and 21 pet 0, vs. prediction -; The target matte grade was varied by varying the solid injection rate while keeping the same gas rate. Conditions for the experimental runs are given in Hahn and Sohn [1990], from which the figure is adapted.)

ill-

.._

30 (a) so2

(b)

0, We X0, ) (4 0,

30

(b) . . .

so2

g
1)

g E

20

0, (Me, 0, )
II

8 t a

10

0
0

30,

I
( 111 )

20 . (4

Axial

Distance

from

Top

(m)

Figure 8. Comparison of the computed results with measurements along the centerline in an Outokumpu pilot flash furnace wtih a single-entry burner. (0, (MexO,) denotes the percent 0, consumed to produce metal oxides. Conditions for the pilot-plant tests are given in Hahn and Sohn [1990], from which the figure is adapted.)

Axial Distance from Top (m) Figure 9. Comparison of the computed results with measurements along the centerline in an Outokumpu pilot flash furnace with a double-entry burner. (Conditions for the pilot-plant tests are given in Hahn and Sohn [1990], from which the figure is adapted.)

A double-entry burner developed by Outokumpu Oy injects the concentrate particles and the distribution gas with a radial velocity component. Figure 9 shows the comparison between the model predictions and measurements in the Outokumpu pilot plant equipped with such a double-entry burner [Asteljoki, 1987; Hahn and Sohn, 19901. Although the measured data are somewhat scattered, the overall agreement is satisfactory. The comparisons presented above [Yasuda and Sohn, 1995; Hahn and Sohn, 19901 remain the only experimental verification of a mathematical model of the flash smelting process to date in terms of particle dispersion, the degree of reaction, and gaseous concentrations. Figure 10 shows the predicted contours of the particle concentration in the same pilot furnace [Sohn, 19911. Here, the particle number density normalized to the inlet value is plotted as a function of the radial and axial positions. The top graph is for the case of a single-entry injector with only an axial velocity component at the burner tip; the bottom graph is for the case of a double-entry burner in which the solid particles are given a radial velocity component at the burner tip. We can see that for a single-entry system, the particles tend to be concentrated near the centerline. In the latter case, the 20

particles are very uniformly dispersed throughout the furnace volume. Figure 11 shows the predicted contours of the 0, and SO, concentrations and the gas temperature for a commercial Outokumpu flash furnace with radial particle feeding [Hahn and Sohn, 19901. The most notable aspects of the predictions for a flash-smelting furnace are:

(1) By giving a radial velocity component to the solid particles at the burner tip, particle dispersion becomes more uniform in the furnace (Figure lo), and thus, a larger portion of the furnace volume can be utilized for smelting. This is consistent with the new burner developed by Outokumpu. A reliable mathematical model provides quantitative information regarding such otherwise qualitatively apparent effects. (2) The chemical reaction is essentially completed within a fraction of the total height typically used for most commercial units, as shown in Figure 11.

21

Contours

of Normalized

PartIde

Number

Denolty

There are a number of reasons why the furnace height cannot be as short as what the calculated result would indicate, such as less reactive recycle materials and agglomeration of the feed concentrate. However, the computed results provide the bounds of ideal performance as a target for process improvements. Even under typical current operating conditions, the heights of industrial flash furnaces may, in general, be excessive. In fact, the fact that the height of a commercial furnace can be substantially shortened has been demonstrated by the Hidalgo Smelter of Phelps-Dodge Company (Playas, New Mexico) [Partelpoeg, 19851. They removed the top 10 feet out of the original 45 feet from their furnace apparently without any undesirable effects. The associated benefits, including a reduced heat loss and refractory requirement, need no further mention. Although Hidalgo did this independently of our calculations, this nonetheless provides an example of what a carefully developed mathematical model can provide a basis for an improved design, operation, and process control at a greatly reduced cost; indeed, at a very small fraction of time and costs of doing laboratory experiments, let alone a pilot-plant study or tests in a full-scale facility.

Figure

10. Predicted contours of particle number density normalized by the inlet value in a pilot flash furnace. (a) single-entry burner, (b) double-entry burner. (Conditions are the same as in the Outokumpu pilot furnace discussed in conjunction with Figs. 8 and 9. Adapted from Hahn and Sohn [ 19901.)

Minor Element

Volatilization

contours

Of o2

Concentration

(4

25

contours 0 so,

Concentration

(%)

The computer simulation code of Hahn and Sohn [1990] was applied to the description of minor-element volatilization inside a flash furnace shaft [Seo and Sohn, 19911. The basic premise of the volatilization calculation was that the partial pressures of the minor element species are the equilibrium values at the surface of the molten particles. The rates of volatilization are then determined by the external mass transfer between the particle surface and the bulk gas phase. The authors carried out experiments for the volatilization of Sb and Pb in a large laboratory furnace. Despite the fact that the experimental points were rather scattered due to the complexity of the process and the difficulty of experimental measurement, satisfactory agreement between the predicted and measured results was obtained. Figure 12 shows an example of such a comparison. The minor-element behavior in an industrial flash smelting furnace was then simulated and compared with available data from a commercial operation. Again, reasonably good agreement was obtained.

ioca

1100

Contours

01 Gas

Temperature

(K)

Other Applications

and Developments

This flash smelting model has been applied to the Kennecott-Outokumpu flash converting process [Sohn et al., 19961, and further refinements including 3-D aspects and a recently developed technique for describing particle behavior based on the particlecloud model are being made [Sohn and Perez-Tello, 19971. Other investigations have lately been performed on the mathematical modeling of the flash smelting process. Most of the new simulations involve the incorporation of a 3-D fluid dynamic computational package to flash smelting conditions. Jokilaakso et al. [1994] presented the results of a comprehensive computational effort to describe the fluid flow patterns in the entire flash smelting furnace system, including the concentrate burner, the reaction shaft, the settler

Axial

Distance

from

Top

(m)

Figure

11. Predicted contours of SO, and 0, concentrations and temperature in an industrial flash-smelting furnace with a radial distribution cone. (Adapted from Hahn and Sohn [1990].)
22

23

l.O-

-----

Pmd.As

Pmd.Sb

----_--.
--

Prer. 6,

Pmd. Pb

Figure
0.2 0:4 0:6 i:o 0:6 Axial Dlstanu from qurnmr Ilp (m) 112

13. Computed velocity vectors of gas and particles near the burner of a flash-smelting furnace. Left: gas; Right: particles. (Adapted from Jokilaakso et al. [1994].)

Figure

12. Comparison between experimental and computed results for the elimination of minor elements in a flash furnace shaft. (Adapted from Seo and Sohn [1991].)

free board, the gas uptake shaft, and the waste-heat boiler. Figure 13 shows an example of the computed gas and particle velocity vectors near the concentrate burner equipped with the Outokumpu distribution cone. Typical velocity vectors at the centerline of the uptake shaft are shown in Fig. 14. The conclusions they drew from their computational work were as follows:

contacting arrangements used in these processes. The various thermodynamic equilibrium models, while very useful in describing the distribution behavior of the species in the system, do not provide any capability in terms of the required size or configuration of the reactor. An example of the attempt to address this problem is the work of Iyer and Sohn [1993; 19941. They analyzed the fluid flow and mixing characteristics in a metallurgical channel reactor with countercurrent liquid flow and high-strength bottom gas injection, such as the QSL leadmaking reactor. Based on the experimentally measured residencetime-distribution behavior, they modeled the channel reactor using an ideal reactor network. A schematic representation of a channel reactor and the corresponding idealreactor-network model are given in Fig. 15. The procedure for scale-up and mass transfer calculations has been described using as an example the zinc transfer between a copper matte and slag under smelting conditions [Iyer and Sohn, 19931.

(9

Gas flow can reliably be predicted using a commercial software, but the calculation of heat transfer dominated by radiation involving dustladen gas is more difficult and less reliable. spreading of particles increasing size. in the reaction shaft improves with

(b) The

The cc>

gas is cooled very rapidly in the waste-heat must be validated

boiler. experimental

(4

Model predictions observations.

against

Jorgensen et al. [1995] also used a commercial 3-D fluid flow calculation package to simulate a nickel flash furnace with four burners. The fluid flow aspects of the model were validated against observations in cold air and water models. They also obtained satisfactory agreement between the predicted and measured particle and gas temperatures in a commercial reaction shaft.

IV-2.

Bath Smeltine

Processes

Figure 14. Computed velocity vectors along the centerline of the uptake shaft of a flash-smelting furnace. (Adapted from Jokilaakso et al. [1994].)

The greatest challenge in the process modeling of bath smelting processes is in developing a simulation model which is helpful in designing a reaction vessel. This is because of the difficulty in quantitatively analyzing the transport phenomena among the molten (often involving more than one molten phase) and gaseous phases in various

24

25

thermodynamic processes.

knowledge

to develop

a complete

process simulation

for bath smelting

IV-3.

Thermodynamic

Eouilibrium

Models

Light Liquid

These models assume that all bulk phases are at equilibrium at a given instance. As materials flow through various phases, their compositions vary in such a way that equilibrium is established continuously. Kellogg [1967] first applied this concept to the zinc fuming process by taking successive finite process steps. Nagamori and coworkers [1978; 1982; 19941 used this approach extensively to describe batchwise copper smelting and converting processes. The application of the concept of instantaneous equilibrium has been extended by Kim and Sohn [1996; 1997; 19981, who eliminated the assumption of stepwise progression of the process by considering the continuous nature of the changes. The two approaches converge when the finite steps taken in the earlier approach are made infinitesimally small. They applied this modified equilibrium method to the description of the two stages of copper converting [Kim and Sohn, 1996; 19981 and copper converter slag cleaning [Kim and Sohn, 19971. Application of the equilibrium modeling approach to the smelting of complex sulfides [Flynn and Morris, 1987; Robertson et al., 19931 and a countercurrent multistage reactor system [Flynn et al., 1987; Robertson et al., 19931 have been described.

IV-4.

Minor-Element

Behavior

in Sulfide Smelting

Figure

15. A schematic representation of the flow pattern in a countercurrent channel reactor and the corresponding ideal-reactor-network model of the material flow and mass transfer (Adapted from Iyer and Sohn [1993]).

In most sulfide smelting systems the viability of a new process is often determined by the degree of metal loss to slag as well as its ability to remove minor elements to slag. Recently, however, the feasibility for the volatilization and recovery of minor elements is increasingly becoming of interest [Hino, 1995; Lehner, 19951. Because of these two reasons, the accurate measurements and modeling of the metal and minor-element distribution among the gas, slag, and matte/metal, especially applicable to the conditions of the new and/or improved processes described above, have been actively pursued in the last two decades. (See references cited in Sohn [1997b].) For describing the minor-element behavior as part of an overall process simulation model, the above-mentioned thermodynamic equilibrium model has been used extensively. Notable examples are the work of Nagamori and coworkers [ 1982; 19941 and Kim and Sohn [1996; 1997; 19981. The only known exceptions in which the minorelement behavior is modeled based on a more complete process simulation including kinetics, fluid flow, and heat/mass transfer are the work of Chaubal et al. [1989] and Seo and Sohn [1991]. They described the volatilization of minor elements in a flash furnace shaft based on the temperature, po, and pso profiles as well as particle composition and distribution in the reactor calculated first u&g a simplified model of particle oxidation [Chaubal et al., 19891 and subsequently from the comprehensive flash smelting model discussed earlier [Hahn and Sohn, 1990; Seo and Sohn, 19911.

Another example of modeling processes involving gas, slag, matte, and metal phases has been put forward by Robertson (19951. This approach is based on the assumption of interfacial equilibrium, which is computed by an equilibrium solver. The reaction rates are then assumed to be controlled by mass transfer between the bulk phase and the interface. For multiphase systems, the coupled mass transfer rates between various phase pairs and the bulk material flows through different phases are computed using software such as METSIM. Although this approach has so far been largely applied to steelmaking operations, it should be applicable to sulfide smelting with appropriate modifications. The vast literature information on the characteristics of gas bubbles and jets injected into melts has not fully translated into the process modeling, at least in the sulfide smelting field. The sizing and design of sulfide bath smelting reactors are largely based on an empirical or semi-empirical approach [Themelis and Mackey, 19921. It appears to be a challenging and potentially fruitful task to combine the powerful computational fluid dynamics techniques, bubble and jet characteristics, and mass/heat transfer processes with

IV-j.

Phvsical and Thermochemical

Data Base without a reliable Although various

Reliable process modeling and simulation cannot be accomplished fundamental data base for physical and thermochemical properties. 26 27

standard sources for compilations of these properties exist, their determination has continued. Some properties have been measured repeatedly to obtain more accurate data as improved instruments and experimental techniques became available. Other measurements have been made as new materials are developed. These measurements have been collected as part of annual reviews of worldwide literature dealing with the basic principles of metal extraction [Sohn, 1976-1992; Sohn and Cho, 1993-19971.

Kennecott is designed to produce a tail gas containing less than 100 ppmv sulfur dioxide and actual emissions are typically in the 40 to 60 ppmv range. These levels are similar to those achieved by scrubbing acid plant tail gas, using lime, caustic soda, or basic aluminum sulfate, as is done in Japan. Although never commercialized, investigations to produce elemental sulfur from SO, gas have been carried out. Examples include ASARCOs pilot-plant work in the early 1970s and the U.S. Bureau of Mines work on a citrate process [Weisenberg et al., 19801. More recently, DellAmico et al. [1997] presented a two-stage reaction scheme to convert SO, to elemental sulfur through reaction with pyrrhotite. Emissions from molten metal handling remain one of the major challenges for smelting. Recent studies in Europe and elsewhere have shown that molten matte and slag emit significant quantities of heavy metal fume containing arsenic, cadmium, lead and zinc as well as sulfur dioxide. Control of these emissions will challenge the industry, particularly smelters with Peirce-Smith converting. Emissions of heavy metals is a rising concern from both the standpoint of employee exposure and emissions into the Better containment of these emissions and application of particulate environment. removal equipment is becoming increasingly important. This in turn favors processes that can be tightly sealed, fixed furnaces over rotating furnaces, and fewer vessels. Again, ladle and crane handling of molten matte, slag and metal requires costly emission controls to have any hope of achieving low emission levels comparable to continuous smelting and converting processes. The better containment of heavy metals and the progressive tightening of solid waste disposal regulations, in addition to the use of more impure concentrates and recycled dusts, are resulting in increased levels of deleterious minor metals in anode copper. Several new processes for the treatment of furnace dusts and acid plant bleed streams have been developed to provide a controlled outlet for these elements in an environmentally responsible manner. The lead industry has also channeled considerable resources in capturing sulfur as sulfuric acid. Typically, a single-contact or double-contact sulfuric acid plant is used for this purpose. The emissions are dilute SO, gas streams from the sinter machine and blast furnace and acid plant tail gas. The overall sulfur capture is over 90%, and no desulfurization of acid plant tail gas is known to the authors. In view of the relatively high vapor pressures of Pb, PbO, and PbS at operating temperatures, the ambient air quality in lead smelters and refineries has been a major Considerable money has been spent by a major nonferrous environmental concern. smelter at two of their lead smelters to meet the ambient air quality of 1.5 &m (quarterly average; monitored every 6 days for 24 hours using a Hi-V01 sampler). Both of these smelters are in compliance now. A lead refinery was recently closed due to the enormous costs of engineering controls needed to meet ambient air quality standards. The only pyrometallurgical operation involved in the recovery of zinc from sulfide concentrates is the roasting to produce ZnO calcine and SO,. The sulfur capture is essentially in the form of sulfuric acid. However, with the Sherritt Gordons pressure leaching of zinc concentrate, the sulfur capture is now in the form of elemental sulfur. In the Imperial smelting process, the sulfur is invariably captured as sulfuric acid, with sulfur recoveries exceeding 90%.

V. ENVIRONMENTAL

ISSUES

As mentioned in the opening remarks, the change in environmental awareness, around the world, has perhaps been one of the most dramatic drivers in the industry. Enviromental issues and energy consumption, which are not unrelated, was clearly a major focus during the 1983 International Sulfide Smelting Symposium. Since then, the industry has shown growing international awareness concerning not only emission of sulfur dioxide but also heavy metals, water pollution, and the important topic of worker hygiene. Sulfur dioxide emissions from the smelting industry have decreased considerably since the 1983 Symposium. Many smelters that formerly had no sulfur fixation equipment now have installed sulfuric acid plants. Countries such as Canada, Mexico, Chile, and Peru, where emissions were virtually uncontrolled, are now adopting progressive regulations. In part, this is due to international and domestic environmental movement pressure. Financing of dirty products is becoming more difficult. Some major international environmental mining companies have adopted policies that promote a responsible approach to environmental issues in general. Finally, in countries such as Chile, where agriculture is fast becoming a rival to mining and smelting, the adverse local effects of high emissions of sulfur dioxide and heavy metals are simply uneconomic. Tighter controls are being implemented to protect the agricultural industry. Advances in sulfur oxide control have been few. Earlier focus on scrubbing dilute sulfur dioxide gas from reverberatory furnaces has nearly been abandoned because of economics. It has, for the most part, been more cost effective to replace aging fuel-fired or electric reverberatory furnaces with modern autogeneous and oxygen-fed smelting processes. In spite of this trend, the capture and treatment of Peirce-Smith converter off gas remains a serious problem. Many smelters simply find the cost for capture and control of these dilute and cyclic gases too expensive. Even when controls are applied, the cyclical nature of the gas flows results in accelerated aging of acid plant and relatively high operating and maintenance costs. These factors have, in turn, led to a major effort to develop continuous converting. The level of sulfur capture has steadily increased over the last fifteen years with many more smelters now achieving over 98% capture. The highest level of sulfur capture is now by the Kennecott Utah Smelter where overall sulfur capture of 99.9% has been demonstrated. At this level of capture, it is more meaningful to express sulfur emissions in terms of kilograms of sulfur dioxide per tonne of metal product. Using these criteria, the Kennecott smelter emits less than 3.5 kg/tonne of copper, the lowest level of any smelter in the world. A key to achieving very low levels of sulfur dioxide emissions is the development of ultra-low emission acid plants. The new Monsanto Enviro-Chem acid plant at 28

29

A growing concern for the industry is the movement to ban copper, nickel, lead, and other metals from normal human contact. This extreme environmental movement is based on poor science that claims to show serious health effects from even very low-level exposure to metals. Even metal coinage is suspected. It is obvious that the effect of any irrational ban on metals would have an effect on the sulfide smelting industry that would be far greater than all of the previous environmental and energy considerations.

even very high levels of emission control are greatly reduced because of the scale and the ground upldesign for maximum achievable-control technology. Sulfuric acid plants in particular can now be build to emit less than 100 ppmv sulfur dioxide in the tail gas compared to a more typical level of between 300 ppmv and 650 ppmv S02. Similar emission reductions can be engineered into new facilities. Many technical challenges cost for cleaning copper smelter Advances in understanding the the flow and mixing patterns in remain. One of the most important is slag cleaning. The slag can easily amount to 15% of the total smelting cost. entrainment and dissolution of metals in slag including furnaces are critical.

VI. VI-l. Smelting

A VIEW

OF CHALLENGES

FOR THE INDUSTRY

In spite of the recent technical advances in the industry there are still many smelters that are marginal with respect to productivity, emission control, and costs. Productivity is difficult to quantity due to the huge range of work practices and education levels across the various regions, but one thing is clear: As industrialization increases, productivity usually increases but at a high cost. The long-term competitiveness of inefficient smelters must be viewed as suspect. Emission control is an equally difficult force to quantify. Old dirty smelters, particularly large ones, are often such a significant factor in local, regional or state economies that imposition of tight emission control standards will likely occur at a very slow pace, perhaps even an imperceptible one. Indeed it may take several more decades for the truly dirty smelters to be replaced, and that is more likely to be due to depletion of ore resources than regulatory pressures. Operating costs, including the cost of capital, are perhaps the largest factor in the advancement of newer technologies and replacement of old smelters. Since many if not a majority of smelters process concentrates for others, the health of the custom smelting industry is critical. Small-capacity smelters are increasingly marginal if local, de-facto subsidization is not a factor. Custom smelters in Japan, Europe, the U.S. and Korea are increasingly disadvantaged by high labor costs, high energy costs and very restrictive environmental initiatives which force operation of costly tail-pipe emission control equipment. The fundamental economics of custom smelting are sufficiently marginal that construction of new facilities is not clearly economic. Incremental expansions of existing smelters are still attractive, but the opportunities for further expansion are diminishing. Ultimately, many custom smelters constructed in the 1970s or even earlier will likely become uneconomic. A change in national policy, exemplified by the demise of aluminum smelting in Japan, has resulted in the closure of entire industries with replacement capacity financed elsewhere. It is likely that copper smelters, and to a lesser degree nickel smelters, will need to get much larger to just@ the expenditure for a new facility. Consolidation of smelting capacity at a single site would serve to reduce the investment cost per ton and provide the critical mass to justi+ the highly skilled technical team needed to run advanced technologies. The recent construction of very large, single-line advanced copper smelters such as the Kennecott smelter in Utah would appear to set the stage for rationalization of the industry. Copper smelters with capacity in excess of 500,000 tonnes of copper per year (say 1.5 million to 2.0 million tonnes of copper concentrate per year) are now clearly technically feasible and in fact do not require any pioneering engineering. The cost for

While flash smelting furnaces achieve long campaign life, other processes are not so well positioned. Improved refractories, improved protective cooling, and improved process control are all fundamental to process optimization. Sensor development is particularly important, given the highly aggressive environment in smelters. I Understanding concentrate burners in flash smelting and melt-gas behavior in bath smelting processes is work that is still at its infancy. Computational fluid dynamics (CFD) modeling has really just begun. Integration of smelting, both upstream and downstream, to optimize the entire metal production train has not advanced very far. With the successful development of Solid Matte Oxygen Converting, the possibility now exists to install mine-site smelters to produce high-grade matte for shipment to a central converting and refining facility and The cost for transporting the copper sulfuric acid for use in copper leaching. concentrates is high, sometimes approaching 10% of the contained metal value. This cost could be reduced by a factor of 3 to 4 by producing high-grade matte instead of concentrate. Anode breakthrough casting and electrolytic refining remains an inefficient process. in this area could have a significant effect on overall profitability. A

VI-2.

Alternatives

to Smelting

Hydrometallurgy has been touted as the logical replacement for smelting for the last To date all attempts to develop a practical and cost-effective forty years. hydrometallurgical process have generally met with failure. One problem for hydrometallurgy is the inherent efficiency of smelting. What other process can treat the raw concentrates as a valuable fuel to heat the furnaces using only oxygen from the air, produce an innocuous waste (slag) that can be easily disposed of on land, convert the sulfur to a valuable by-product (sulfuric acid), and achieve nearly 100% metal recovery all in a relatively simple two-step process? The down-side of smelting and refining includes difficult containment of molten materials, severe conditions that mandate close control and skilled technical staffs, large inventories of metal in process in the refinery, and the general perception that the industry is dirty. Advances in pressure autoclaves, solvent extraction and electrowinning may allow some special concentrate types to be processed to metal using hydrometallurgy. It is more likely that some hybrid process will be developed.

VI-3.

Substitution

Substitution remains a major problem for all metals. More efficient communication equipment is reducing the use of copper, but the industry is growing so rapidly that Still, further advances in optical fiber and wireless overall consumption is increasing. transmission could threaten copper. Electrical applications remain the largest use of copper. No effective substitutes are emerging, but more efficient use of electrical wiring will increase the efficiency of use.

which to support R&D activities. But it may be a good time to ask whether the industry can maintain its competitiveness and health without the foundation of young metallurgists and continued innovation based on R&D output.

VII.

CONCLUDING

REMARKS

VI-4.

Metal Toxicity

An emerging but radical environmental thrust in Europe and elsewhere is calling for a near total ban on the use of copper, nickel, lead, and other metals based on the mistaken conclusion that even minute exposure to these metals can cause a wide range of adverse health effects. Coinage and culinary water piping in particular are being singled out because of their universal use. Sadly, the movement is highly political and decidedly anti-industry. Nonetheless, some governments are entertaining much more restrictive regulations, although there is a near total absence of credible scientific evidence. Improved awareness and education against this troublesome movement are critical.

Since the first International Sulfide Smelting Symposium held in 1983, considerable progress has been made by nonferrous smelters all over the world in adopting new technologies in the areas of smelting, sulfur capture, and environmental controls. There has been a tendency to build relatively large plants (-300,000 tpy Cu) or modernize existing plants to increase capacity in order to reap the benefit of the economy of scale. With the increase in plant size, the development and adoption of continuous processes have become increasingly important. Examples of this important trend were discussed. However, the goal of a single-stage smelting and converting process remains elusive. Advances in sulfur capture and other pollution reduction in the smelting industry were summarized. At present, no hydrometallurgical process is on the horizon to compete with sulfide smelting. However, many are under evaluation and may have a place for production of small amounts of copper at remote locations. It is hard to envision a hydrometallurgical process for copper concentrates that would produce tonnage copper as is done today with sulfide smelting. However, the same cannot be said of lead and zinc plants. The notable advances made in basic R&D in the field of sulfide smelting were reviewed, including the various developments in process modeling and computer simulation. The greatly increased capability to describe, analyze, and simulate the previously intractable, complex pyrometallurgical processes was illustrated with examples. This has become possible thanks to the accumulated knowledge in basic principles consisting of thermodynamics, kinetics, and transport phenomena as well as the availability of fast computers that can solve, within a reasonable amount of time, the complicated governing equations that describe these complex processes. Just when such capabilities are becoming available, however, it is unfortunate that the support to educate and train young engineers in the pyrometallurgy discipline as well as to carry out R&D work is dwindling drastically. The resulting shortage of qualified personnel and stagnation of technological development are feared to bring about serious consequences to the industry. Other challenges the industry faces from within and without were also discussed.

VI-S.

Shortage

of University-Educated

Manpower

and Basic-Research

Output

The most serious challenge of all that the industry may face in the future is the serious diminution of supply of young engineers and basic research results from academia. Among the factors that have contributed to this situation are:

(1) the

tremendous decrease of students interest in metallurgy as their career choice and the reduction in resources with which academic programs can attract them by providing scholarships and other incentives, complete disappearance in the U.S. and substantial decrease elsewhere of governmental support of education programs and academic research in the field of primary metal production, and to fill the void left by such

(2) the

(3) the

industrys inability or reluctance greatly reduced public support.

Under the current atmosphere, there will be preciously few young metallurgists coming out of universities that are educated and trained in the field of chemical and process metallurgy in general, let alone in pyrometallurgy or smelting in particular, unless the industry recognizes this and starts investing resources in both undergraduate and graduate programs. Furthermore, the type of pioneering basic research carried out by prominent metallurgists mentioned earlier in the paper, from which the metallurgical industry has benefited greatly, will no longer be available without industrys infusion of support for basic research both within the industry and in academia. It is understandable that, having gone through the belt-tightening lean years in the 198Os, the industry has lost much of the infrastructure and indeed maybe its will, through
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36

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