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By Mototsugu Matsuno

A new process has been developed to treat fly ash generated from municipal incinerators, which contains not only toxic metals such as lead and cadmium, but also dioxins. The process includes the following steps; fly ash is formed into green pellets with some additives and the pellets are then roasted to eliminate or stabilize the toxic metals and to decompose dioxins. A pilot plant with a capacity of approximately 100 kg/hr was used to test the process, The tests verified that heavy metals were either volatilized or stabilized and dioxins were decomposed by high-temperature roasting. The pelletized ash was found to be non-toxic, so that it can be recycled as artificial lightweight aggregate. It was also found that volatilized metals collected as secondary ash can be recycled as smelting resources.

Jan 1, 2003

By A. Cullaj

Several industrial sites suffer from the contamination of soils from heavy metals, which are emitted among others by anthropogenic mining and metallurgical activities. Effective and economic physicochemical technologies for remediation of these sites remain complicated and costly. A new alternative remediation technique is the so-called phytoremediation. This is based on the ability of some plants to accumulate very high concentrations of metals from soils and thus providing the basis for a remediation of the contaminated sites. This technique as an emerging branch of natural biotechnology, has several advantages compared to the sophisticated physicochemical techniques of soil remediation. It is not only environmentally friendly but also its costs are quite low since it is solar driven. Furthermore plants can accumulate metals to such levels that the mineral recovery maybe feasible even in conventional Ni refinery or smelting operations. n this work, the potential of many plants to accumulate nickel has been investigated in order to identify the species which offer the best phytoremedial potential for nickel contaminated soils in Albania. Field surveys have been made in five nickel-containing sites in order to identify the nickel tolerant species that have spontaneously grown in contaminated soils. Atomic Absorption Spectrometry measurements were carried out on 145 different plants collected. 16 of them were identified as having an hyper ability to accumulate nickel since they contained more than 10 000 mg Ni per kg (OW). Seven taxa are of Alyssum genus and one of BornmueIIera genus of Cruciferae. The highest accumulation of nickel was present in aerial parts of Alyssum murale var. chlorocarpum Hausskn (25 500 mg/kg or 2.5%) and Alyssum markgrafii O.E. Schulz (23 700 mg/kg or 2.37%). The seeds germinated are more evidenced at A.m.var. chlorocarpum, about 63%. These plants are suggested as the most promising species to be used for phytoremediation purposes in nickel contaminated soils and phytoextraction of nickel.

Jan 1, 2003

By Xinghui Meng

The recovery of platinum and palladium from automotive catalysts has been investigated by leaching in iodide solutions with oxidants including oxygen and iodine in an autoclave. An ammonium salt was presented in a neutral leaching solution as a key leaching reagent to achieve high recoveries of the platinum group metals (PGM). The effect of temperature, and concentrations of oxidants and of ammonium salt on the recovery of PGM was examined. Under the experimental conditions studied, the recovery of platinum and palladium was found to be greater than 95%. An economical assessment of this process has also been examined and discussed.

Jan 1, 1995

By Rainer Schmid-Fetzer

"Isothermal solidification can be used to form strong bonds at low temperature which remain solid at much higher temperatures. The exploitation of this principally known technique for new high temperature processing steps and applications in electronic assemblies is the aim of this study. Three basically different variants of this bonding process are given. A comprehensive metallurgical screening is performed and the feasibility of binary material systems is given on a quantitative scale. Very attractive systems are spotted that have never been studied before. Detailed examples for the realization of bonding with complex ternary and multilayer systems are given. A highly innovative example is the chip stack or wafer to wafer bonding of unmetallized Si or SiC at 250°C. The proposed bond remains stable above the melting point of Si and enables entirely new semiconductor manufacturing steps. An improved die bonding process was proposed and verified experimentally.1. IntroductionIsothermal solidification can be applied to form strong bonds at relatively low temperature which remain solid at higher temperatures. The general principle of this type of joining processes is illustrated in Fig. 1. An interlayer of a low melting component, Lo, is provided as a foil or a thin film coating between the high melting joint components, Hi. The assembly is heated under moderate pressure to the bonding temperature, T 8 , and a liquid filler forms, either because the melting point of Lo is exceeded or due to a eutectic reaction between Lo and Hi. This molten filler initiates a rapid interdiffusion or reaction diffusion between Lo and Hi and the subsequent approach to an equilibrium state results in isothermal solidification. The solid phases formed at T 8 in the joint region exhibit a remelt temperature above T8 •"

Jan 1, 1996

By A. Cullaj

Several industrial sites suffer from the contamination of soils from heavy metals, which are emitted among others by anthropogenic mining and metallurgical activities. Effective and economic physicochemical technologies for remediation of these sites remain complicated and costly. A new alternative remediation technique is the so-called phytoremediation. This is based on the ability of some plants to accumulate very high concentrations of metals from soils and thus providing the basis for a remediation of the contaminated sites. This technique as an emerging branch of natural biotechnology, has several advantages compared to the sophisticated physicochemical techniques of soil remediation. It is not only environmentally friendly but also its costs are quite low since it is solar driven. Furthermore plants can accumulate metals to such levels that the mineral recovery maybe feasible even in conventional Ni refinery or smelting operations. In this work, thc potential of many plants to accumulate nickel has been investigated in order to identify the species which offer the best phytoremedial potential for nickel contaminated soils in Albania. Field surveys have been made in five nickel-containing sites in order to identify the nickel tolerant species that have spontaneously grown in contaminated soils. Atomic Absorption Spectrometry measurements were carried out on 145 different plants collected. 16 of them were identified as having an hyper ability to accumulate nickel since they contained more than 10 000 mg Ni per kg (DW). Seven taxa are of Alyssum genus and one of Bornmuellera genus of Cruciferae. The highest accumulation of nickel was present in aerial parts of Alyssum murale var. chlorocarpum Hausskn (25 500 mglkg or 2.5%) and Alyssum markgrafli O.E. Schulz (23 700 mg/kg or 2.37%). The seeds germinated are more evidenced at A.m.var. chlorocarpum, about 63%. These plants are suggested as the most promising species to be used for phytoremediation purposes in nickel contaminated soils and phytoextraction of nickel.

Jan 1, 2003

By Eddie C. Chou

Phelps Dodge, Inc. (PD) is currently developing a lateritic nicke/Vcobalt deposit in Madagascar. Hazen Research, Inc. provides technical assistance to PD to investigate recovery processes for nickel and cobalt. Various process options were evaluated in laboratory experiments and pilot plant operations. The process selected for the feasibility study consists of feed preparation, high-pressure acid leach, countercurrent decantation wash, sulfide precipitation, sulfide dissolution, solvent extraction, ion exchange, and electrowinning. Among these unit processes, high-pressure acid leach, sulfide precipitation, and sulfide dissolution are applications of pressure technologies. Process development work and design criteria for commercial operations of these unit processes are presented in this paper. Concerns related to scaling in the high-pressure acid leach and the sulfide precipitation processes are discussed. Corrosion of various metal coupons under these environments was examined.

Jan 1, 2000

By G. T. Lapidus, O. J. Solis-Marcial

"The oxidative dissolution of copper from refractory minerals, such as chalcopynte, represents a technological challenge that has occupied hydrometallurgists for more than half a century. Innumerable processes have been suggested, but the majority operates at high temperatures or employs corrosive media. The origin of this refractory nature is the formation of passivating phases of iron(III) or copper. One option is to add non-corrosive ligands that complex these metal ions, thereby facilitating their dissolution. In the present work, the effect of acetone in sulfuric acid solutions was studied. The initial experiments were on chalcopynte carbon paste electrodes using cyclic voltammetry, where greater reactivity was observed. Later, leaching tests with hydrogen peroxide, cupric sulfate and ozone and, as oxidants, were performed. High extractions were achieved in three hours at 50°C. The solid residues contained the iron in the form of Fe203 and FeOOH.IntroductionChalcopyrite is the most important mineral of polysulfide copper ores [1] and accounts for approximately 70% of the world's copper reserves [2]. Currently, the copper present in chalcopyrite is extracted mainly by pyrometallurgical processes, which generate environmental concerns because of the formation of SO2 gas and submicron particulates [3]. The development of a less aggressive hydrometallurgical process for the extraction of copper would constitute a possible solution to these problems. For that reason, studies of the dissolution behavior of chalcopyrite are of great technological importance [4], However, the proposed oxidative leaching routes for chalcopyrite, generally at high pressures and temperatures, have not been implemented on an industrial scale, because of the elevated costs required to equal the high copper extractions obtained in thermal processes. These extreme leaching conditions are required because of the refractory nature of chalcopyrite. Passivation has been used to explain this phenomenon, although researchers have disagreed on the composition of the layer, which is various have assumed to be sulfur, copper sulfides, and iron-bearing jarosites or hydroxides [5]. If the latter compounds are the cause, an alternative solution would be the use of polar organic solvents in the oxidative leach to decrease the formation of the passivating iron layer. In this work, the influence of acetone on the oxidative leaching of a chalcopyrite concentrate at room conditions is explored."

Jan 1, 2012

By Randall M. Gennan

Generally sintering is focused on the bonding of particles at high temperatures; possibly with simultaneous densification. However, an important aspect of sintering occurs during heating at relatively low temperatures where polymer processing aids are removed via control of the atmosphere, heating rate, or hold time at intennediate temperatures. New insights into burnout processes show impact from the polymenype, particle size, amount of polymer, atmosphere, part geometry, and thermal profile. This presentation focuses on the key parameters to demonstrate improved mechanical property levels are available in traditional powder metallurgy alloys by proper selection of the processing polymer and proper care in its thermal extraction. The focus is on mechanical property, where gains up to 40% are demonstrated due 10 changes in the processing polymer. Further, atmosphere control during polymer burnout provides a benefit by allowing formation of desirable carbonitrides, giving strength levels over 3 GPa (over 400 kpsi). Insight is? gleaned from powder injection molding, where high polymer contents mandate proper processing control.

Jan 1, 1996

By Riyad N. Ahmad-Bitar, Shadia J. Ikhmayies

"CdS/CdTe solar cells were built by depositing a 200 nm layer of Sn02:F on glass substrates by the spray pyrolysis (SP) technique, a 500 nm CdS:In layer by the same technique and a 1-1.5 µm CdTe layer by vacuum evaporation. The cells were CdCh heat-treated in nitrogen atmosphere for 30 minutes at 350 -.C. The photoluminescence (PL) spectra were measured at the CdS/CdTe interface for two cells with different values of the CdTe layer's thickness at temperature T = 60 K. A deconvolution peak fit was performed from which it is found that the peaks are characteristic of the solid solution CdSxTei-x· The parabolic relation that relates the bandgap energy with the composition was used to estimate x, where xis [S]/([Te]+[S]) and [Te], [S] are the concentrations of Te and S atoms respectively. The results show that the interface is smooth and the change of the bandgap occurs gradually.IntroductionCdS/CdTe heterojunctions represent a combination of materials promising various applications, and for solar energy conversion in the first place [1]. In photovoltaic cells the CdS material acts as a wide bandgap window. Direct bandgap CdTe with high optical absorption coefficient is used as an absorber [1]. Solar cells with efficiencies of 10 to 16% have been obtained with CdTe grown by close space sublimation, electrodeposition, vacuum evaporation and rf sputtering methods [2]. In this work the CdTe layer was prepared by vacuum evaporation because it results with films of minimum impurities, while the Sn02:F and CdS:In layers were deposited by the spray pyrolysis technique because it is a low cost method which enables intentional doping and large area thin films."

Jan 1, 2011

By Pengfu Tan

In order to understand and control the formation of dioxins and furans in iron ore sinter plants and to possibly avoid expensive end-of-pipe removal stages, thermodynamic calculations on the stability of PCDD/Fs have been combined with sinter process modeling by means of kinetic simulations and computational fluid dynamics. Three thermodynamic databases of PCDD/Fs, derived using the Group Additivity approach and two computational molecular modeling methods, MNDO and PM3, respectively, combined with the SGTE database have been used to model the PCDDIF formation and the PCDD/F isomer distributions in iron ore sintering. The results show very similar conditions for the PCDD/F formation using the different databases. Concerning the isomer distributions of toxic PCDD/Fs, the calculated data derived from the MNDO method showed optimum agreement with measured values from industrial furnaces. The thermodynamic calculations also proved that the isomer distributions found in combustion processes are equilibrium values, while the concentration ratio of PCDDs and PCDFs in the wind boxes does not represent an equilibrium state. A CFD model of iron ore sintering was developed including the kinetics of 15 relevant chemical reactions with the aim of describing the temperature fields and the gas flow patterns in the sintering bed. On the basis of these information and experimental observations reported in the literature possible pathways for the PCDD/F formation in sinter plants have been identified: PCDD/Fs are formed in the critical temperature region of 250 to 450°C below the combustion zone, are then carried downwards with the gas and condensed close to the bottom of the sinter bed. Transported to the discharge end with the solid mixture, they are again released into the gas phase when the flame front approaches the bottom. PCDD/Fs are also formed in the last wind boxes when the hot off-gases cool down and reach the critical temperature range. Consequently, methods to reduce the dioxin formation reactions are proposed including inhibitor addition to the sinter feed and off-gas quenching.

Jan 1, 2003

By R. G. Henley

Mount Isa copper concentrate was combusted in a laminar-flow furnace. The conditions simulated those likely to be encountered in flames in flash smelters of the Outokumpu (air as oxidant) and INCO (oxygen as oxidant) types. The range of conditions studied was as follows: T 400-1400°C, 02 0-100%, SO2 0-95% for residence times up to 0.23 s. The distribution of sulfur, arsenic and lead between the particles and the gas phase was studied. Combustion was very rapid provided the concentrate was adequately dispersed, i.e., no agglomerates. The importance of the latter is discussed. It was possible to oxidize 80% of the sulfur present in the con¬centrate after only 0.1 s reaction time at 1000°C in an atmosphere contain¬ing 8.5% 02 and 12.5% SO2. Best volatilizations (90% of the As, 52% of the Pb) were obtained under localized conditions attained in an air-type flame. Average volatilizations were: air-type flame, As 50%, Pb 32%; oxygen-type flame, As 40%, Pb 30%. The substitution of oxygen for air reduced the arsenic volatilization. The products of combustion were mainly cuprospinel and cuprite; small inclusions of elemental copper were found in some of the particles. At high temperatures, there was a loss of copper due to vaporization of CU( g) CuO kg) (g)

Jan 1, 1983

By Christopher B. Vierrether

Reflected light microscopy, scanning electron microscopy, and electron microprobe analysis have been used to determine the mineralogy, phase percentages, grain sizes, textures, and partitioning of cobalt and nickel in two cobalt-nickel rich mattes. These mattes were prepared by submerged bath smelting from a flotation cobalt-nickel concentrate containing 4.8% cobalt and 5.1% nickel. The concentrate was derived from lead-zinc-copper ores of the Viburnum Trend, southeast Missouri. Eleven discrete phases have been distinguished in the matte samples, three of which contain significant cobalt and nickel. The phases are cobaltpentlandite ((Co,Ni,Fe)9S8), cobalt-bearing marmatite ((Co,Fe,Zn)S), shandite (Ni3Pb2S2), bornite (Cu5FeS4), galena (PbS), magnetite (Fe3O4), pyrrhotite ((Co,Ni,Cu,Fe)1_xS), chalcocite (Cu2S), CuPbS phase, metallic copper, and metallic silver. Cobaltpentlandite and cobalt-bearing marmatite- occur in coarse grains (50 µm) that would separate readily during grinding, but shandite contains small (5 - 10um), abundant inclusions of pyrrhotite and bornite.. Some mineralogical variations between the two matte samples were due to differing degrees of oxidation during smelting,

Jan 1, 1988

By Bo Jiang, Lianyun Liu, Hongmin Zhu, Kai Huang

"Watermelon peel is selected as a novel adsorbent to remove Pb(II) from aqueous solution. A simple saponification process is proposed to modify the peel and the adsorbent is characterized by SEM and FTIR. The effects of pH, contact time, initial concentration of Pb(ll), biosorbent dosage and temperature on adsorption of Pb(II) are investigated. Different models are used to fit experimental data. These models indicate that the adsorption process follows the Langmuir model and pseudo-second-order model. The maximum adsorption capacity obtained from Langmuir model is 1.05mol kg-1 for the prepared sorbent. Equilibrium time is attained in 5-10 min for the studied concentrations. The watermelon peel can be used as an effective and low-cost biosorbent for removal of Pb(ll) from aqueous solution.IntroductionRecently, removal of heavy metal ions from industrial effluents by biosorption has become a very attractive topic, since the more serious pollution issues caused by heavy metals emerge frequently, and more strict requirements for its control are called upon by society [1,2]. In this case, most conventional purification technologies are not suitable due to poor cost-effectiveness [3]. For example, chemical precipitation by alkaline reagents usually can not decrease the metal ion concentration below the permissive levels, and also it will produce a large amount of sludge containing toxic metals. Membrane separation techniques can realize deep purification of wastewater easily, although its operating cost is usually high. Thus, considering the high effectiveness, low cost and free-sludge operation, bisorption has become a promising technique in water treatment [4]. The most important thing for this technology is the synthesis of a suitable biosorbent, whose adsorption properties will determine the removal efficiency and economic cost for the whole process. Watermelon is one of the most popular fruits for mankind for its delicious flavor. Usually, the watermelon is consumed mainly for its edible pulp, and its peel is discarded or only used as feed for livestock. Considering the pectin contained in the watermelon peel, just like that in orange wastes in the reported literatures [3], the idea of using it as the raw material to prepare the biosorbents for heavy metal ions removal from the aqueous solution was evaluated in this study."

Jan 1, 2012

By K. Robinson

Following the longest Smelter campaign in BCL?s history it was planned to completely rebuild the flash smelting furnace in 1987. This was the fourth major overhaul and the most extensive so far attempted. Detailed planning took place over several year$ preceding the shutdown and implementation was completed in 54 days. The key to minimising shutdown time was the method designed for installation of the new uptake shaft and reaction shaft. Major repair work was also undertaken in the waste heat boiler and electric furnaces. Both of these activities had an impact on the critical path of the flash smelting furnace overhaul.

Jan 1, 1993

By Liangying Wen, Feng Xia, Chenguang Bai

"The situation of the Ti-V-Magnetite samples reduced with microwave has been investigated in laboratory. Firstly, the paper focuses on the heating behaviors of vanadium-titanium magnetite and characteristics of carbothermic reduction of V-Ti-magnetite in the microwave field. The effect of concentrate's size, quality on heating behaviors and reduction processes were researched. Results show that microwave heating may be a new heating resource replace of carbonic combustion reaction in reducing reaction. When the allocation of carbon is (16.7-30)%, carbothermic reduction of V-Ti-magnetite in the microwave field can proceed; with the increasing of carbon mixed, the metallization rate increases; and Fe, V can be reduced from their oxides in the microwave field; Titanic low oxide can be reduced from TiO2.1. IntroductionThe resource of Ti-V-Magnetite is abundant in the western area of Panzhihua in China, so far a mineral deposit of 4.64 billion tons have been proved up, it contains 14.75 million tons of V2O S which accounted for 87% of the vanadium and 5.93 hundred million tons of TiO2 accounted for 94% of the titanium resource respectively in China. The previous study proved that the major composition of mineral of the Ti-V-magnetite are Ti-magnetite, limonite, iron spinel, magnesium spinel etc, and the main elements of the Ti-V-magnetite in this area are Fe, Ti, V, Cr, Co, Ni, Ga, Sc etc[1] Due to the restrict of the BF-BOF process technical, during the smelting of the iron, the level of extracting the vanadium, titanium as well as other metal elements is limited. This results serious wasting of resources. To develop a new reduction process of Ti-V-magnetite is on the agenda, the microwave assistant reduction could meets this need, based on its characteristic of easy controlling of heating rate. To make use of the microwave energy to substitute the released heat sources of carbon combustion with air, use the solid phase state reduction at a relative lower temperature, make the beneficial element in Ti-V-magnetite transferred into the metal phase, then separated from the impurity. It is well worth to point out that once the microwave based reduction method has its industrial scale, it will take an outstanding position by its less release of carbon dioxide. This new environment-friendly process will play a vital role in the development of social industry and economy."

Jan 1, 2008

By R. P. Tavares, M. Isac, R. I. L. Guthrie

"The configuration of the metal delivery system used in twin-roll casting can play a significant role in determining both internal and surface quality of the strips produced by this process.In the present work, a mathematical model for coupled turbulent fluid flow, heat transfer and solidification was developed and used in the study of metal delivery systems for twin-roll casting of low-carbon steels. This study was applied to a pilot twin-roll caster being investigated in Canada, with a roll radius of 0.3 m, producing strips of thicknesses from 4 to 7 mm, at roll speeds ranging between 4 and 12 m/min. Various configurations of metal delivery systems were simulated and their effects on the advance of the interdendritic solidification front and levels of turbulence and temperature within the caster investigated. According to the predictions of the model, an extended nozzle with inlet flow towards the surface of the rolls seems to be the best alternative for feeding liquid steel into twin-roll casters.A full scale water model of a pilot twin-roll caster was also built and used to qualitatively validate the predictions of the mathematical model.Various techniques for fluid flowvisualization were applied. In general, the predictions of the mathematical model were in reasonable agreement with the experiments with the water model."

Jan 1, 1999

By Abbas H. Mirza

Arsenic and selenium are found in low quantities together with other metals in several nonferrous metallurgical process streams such as scrubber blowdown solution, acid plant wastewater, gas cleaning plant water, etc. Normally, the other metals in these streams are present as cations and can be precipitated by conventional lime treatment and sulfide polishing. However, arsenic and selenium are invariably present as anions, AsO33-and AsO43 in the case of arsenic and SeO32 and SeO42 for selenium. Conventional lime treatment removes most of the arsenic, but it does not remove selenium. The present paper reviews the processes and technologies developed to date on the removal of arsenic and selenium from metallurgical process streams.

Jan 1, 1996

By Takeshi Nagano

Copper pyrometallurgy in Japan has experienced quite fundamental changes in last fifteen years. The severe environmental restriction coupled with increase of energy costs accelerated the development work of the new continuous process in Mitsubishi Metal Corporation. After several years of pilot plant test work the commercial plant was put into operation at Naoshima Smelter in 1974, the design capacity of which was 4,000 tonnes of copper per month. Many modifications and improvements have been incorporated into the process and 7,200 tonnes per month of copper production was achieved in 1983, proving that continuous process was much more economical than conventional process. It is now possible to design and operate the continuous process in wide range of capacity. This paper will review the process and describe the progress of the process in these 10 years. 311

Jan 1, 1985

By N. L. Piret

Reprocessing of low zinc-bearing residuals with a zinc content of less than 10%, originating from the iron and steel industry, has been given more and more attention in the last few years, due to the potential landfill liability and the increasing cost of disposal by dumping. Whereas, recycling of hazardous electric arc furnace dust is already being performed commercially on a large scale in the U.S., Japan and Western Europe, almost no reprocessing takes place in the case of these low grade zinc-bearing materials. In blast furnaces and basic oxygen furnaces dusts and / or sludges are generated at a rate of 1 to 2 % of the respective production. The technologies for the retreatment of these types of materials, either commercially available or still being developed are briefly described hereafter. They involve internal recycling, upgrading by physical separation methods, separate hydrometallurgical processing and pyrometallurgical treatment. Their scope and limitations are critically assessed in terms of technological applicability, economic feasibility and environmental compatibility. Since, the possibtlity of achieving economic profitability is unlikely with this type of material, the main criteria for acceptability of the treatment process are: generation of a iron-rich material, suitable for treatment by the iron/steel industry, acceptance of the non--ferrous metal-bearing sub-product by zinc smelters, generation of non-hazardous waste materials.

Jan 1, 1992

By Johannes Boonstra

High rate bacterial catalyzed processes can serve to improve hydrometallurgical operations. These solutions are not only economical but also environmental sustainable. With references around the globe, the value of this new approach is recognized by industry worldwide. For instance, metals can safely and economically be separated from process and waste streams using biotechnologically produced sulfide, recovering a valuable metal sulfide product instead of a waste gypsum stream for disposal. Both the natural biological sulfur and nitrogen cycles offer bioconversions that are applied on industrial scale. The shared advantage of these processes is that waste compounds are converted in either a reusable raw material or in a harmless product. This way, natural product cycles can be closed. Applications based upon bioconversions are for example: Sulfur based: Bioleaching, reduction of oxidized sulfur compounds to elemental sulfur, metal recovery with biogenic produced H2S, SO2removal from gas streams, etc. Nitrogen based: Ammonia removal using the anammox-process, biological removal of NOxfrom gas streams, nitrate removal from water streams, etc. Metals: Bacterial processes for the reduction of metals such as uranium, selenium and manganese have proven to offer great potential for clean-up of groundwater streams. This paper contains a description of the above applications. Further, a short introduction on engineered high rate bioreactor systems and a description of industrial biotechnological applications will be provided.

Jan 1, 2003