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The present work is mainly focused on developing intermetallic inert anodes for aluminum electrolysis. The anode alloy based on Al-Ti-Cu system was prepared by casting, followed by the application of a protective coating. Behaviour of corrosion and the passivation under anodic condition was characterized using the electrochemical and microscopic techniques. The results obtained clearly demonstrate that the oxide coating can provide good corrosion resistance via surface passivation of alloy anodes, rendering them inert in cryolite melt.

Jan 1, 2006

By A. Kiziltas, D. J. Gardner, C. W. Mcllwraith, J. W. Bridge, M. L. Peterson

"Dynamic mechanical thermal analysis (DMTA) tests were conducted on high-oil content, paraffin-based wax used in wax-coated granular composites. These composites make up the surface of synthetic Thoroughbred horse racetracks used in North America. The modulus and damping response from the DMTA tests were correlated with the dynamic triaxial shear strength response of the bulk track material taken at two different operational temperatures and at four strain rates. The purpose of these tests is to understand the mechanisms of shear strengthening of the bulk track material as the wax is heated through the first crystalline solid to liquid nominal transition temperature. Previous work using differential scanning calorimetry confirmed that under common operational surface temperatures, the wax coatings undergo distinct thermal transitions. The resulting increase in triaxial shear strength values affects the consistency of the racetrack which, in turn, can potentially affect Thoroughbred racing performance and safety of the track surface.IntroductionSynthetic granular composite materials are being used in nine Thoroughbred horse racetracks in the United States as well as in other tracks around the world. In one case, their use was mandated by the state of California in 2007 due to testimony that these tracks were significantly safer than traditional dirt tracks [1]. Several synthetic tracks have shown substantial reductions in injuries since switching to synthetics; one California track showed a 75% reduction in catastrophic horse injuries during the first year as compared to the previous year racing on a dirt track [2]. The composition of the tracks in the U.S. generally consist of silica sand (>70%), polymer fibers (<5%), and rubber particles (0-15%) all coated with a paraffin-based, high oil content wax [3, 4]. In a recent study of several synthetic racetracks, to include the track location in this study, the oil content ranged from 34 to over 44% by mass [5]."

Jan 1, 2011

By Bora Derin

The partial pressure ratios of sulfur and oxygen for several copper flash smelting plants were derived using the Reddy-Blander (RB) model and predicted dissolved sulfur contents available in the literature. The sulfide capacities (Cs) of six different flash smelting plants (FeO-CuO0.5- CaO-MgO-FeOwAIOl.s?SiO2) slags were calculated. The log (Po2/PS2) versus matte grades of various industrial processes was determined. The PoiPS2 ratio increased with an increase of copper grade. The calculated partial pressure ratios for the copper flash smelting are in good agreement with those of the experimental data.

Jan 1, 2003

By R. G. Reddy

Reduction of different chromite ores with carbon was studied as a function of C/FeO ratio and temperature in the range 700 °C to 1100 °C by thermogravimetry (TGA) analysis. Powders of chromite ore(-150 mesh) and carbon(-150 mesh) were thoroughly mixed in a desired proportions and were placed in the reaction crucible. The reduction rates of reactions were determined by continuously monitoring the weight loss as a function of time at constant temperature using TGA set up. The analysis of results suggest that FeO present in the chromite ores is reduced to Fe involving gaseous intermediates CO and CO2. The overall rate of FeO reduction is controlled by the oxidation of carbon. A kinetic equation, that of random nucleation, was proposed. The activation energies for the reduction of FeO, present in Roast Movat and Transvaal ores, with carbon were determined to be 55800 and 23000 J/mole, respectively. The results of the present study are compared with the data available in literature. The low activation energy values as determined in this study suggest that the carbon oxidation reaction is catalyzed. It is concluded from the present investigation that the low grade chromite ores can be significantly upgraded to higher value added chromite that can be used as a feed source for economical smelting.

Jan 1, 1998

By R. G. Reddy

The Margules .equation is used for interpreting excess Gibbs energy of several ternary systems. In the present study activity coefficient of &apos;a dilute solute, 2, in a binary solvent 1-3 was derived. The derived expression is used to interpret logarithmic activity coefficient of oxygen and sulfur in several metallic systems. Self interaction parameter of the solute is derived from the partial function of solute using constant compositional path. An expression for logarithmic activity coefficient and self - interaction parameter of solute is also derived using Maclaurin infinite series. The derived equation is based on Maclaurin infinite series used successfully to deduce thermodynamics of self interaction of oxygen as a interstitial atom in two metallic systems. The predicted thermodynamic parameters values using Maclaurin infinite series and Margules. equations, are in excellent agreement with the experimental data and also our predictions are far more accurate than the predictions made by other models.

Jan 1, 1996

By Carlos M. Fontes Vieira, Ruben J. Sanchez Rodriguez, Carlos E. Gomes Ribeiro

"The worldwide demand for ornamental stones in building construction is motivating the use of their wastes, generated during fabrication, to produce compound stones. This work has as its objective to investigate the production of an ornamental compound marble (OCM) under vacuum and compression processing of a polyester matrix composite with addition of marble waste as load and as filler. Square OCM composite plates were subjected to compression and flexural mechanical tests. Samples were analyzed to obtain the density and water absorption. The OCM composites presented properties within the expected range of an artificial stone.IntroductionMarble is a limestone, composed mainly of calcite, more or less crystallized by metamorphism that ranges from granular to compact in texture. It has a density 2.7 g/cm3 and its porosity is approximately 0.4%. The UNI 8458 standard defined marble as: ""every crystalline rock constituted mainly by minerals with a Mohs hardness equal to 3-4"". In marble production around70 - 75% of whole extract material is lost in byproducts generation [1,2].In function of large volume of residues generated, the ornamental stones industry has attracted ever more the attention of environmentalists [3].Actually the marble can be pulverized to obtain calcium carbonate for industrial applications. It is also possible to obtain a thinner powder to produce concretes [l]. Some authors study the use of stone residues in concrete mortars and ceramic bricks, getting better properties to these materials [3,4].The marble residues can be also used in engineered stones, or ''agglomerated"" stones, production. The most common engineered stones in the market consist, like a polymer concretes, in polymer matrix composites incorporating petreous components. In the formulation of the engineered stones, the particulate or granular petreous components are the result of fragmentation or trituration processes to which natural stones were submitted to [ 5]."

Jan 1, 2014

By Yun Li

An innovative lead recycling process from scrap lead-acid battery paste is presented. The novelty in the process is avoiding SO2 generation and emission by using reductive sulfur-fixing technique. Iron-bearing secondary wastes produced from metallurgical industry were utilized as sulfur-fixing agent to capture sulfur in the form of FeS (s) instead of generation of SO2 (g). Na2CO3 molten salt was added to the smelting system to speed the reactions and improve valuable metals’ recovery and sulfur-fixation efficiency. Furthermore, this process can simultaneously co-treat various lead and iron-bearing wastes. At the same time, some precious metals, such as Au and Ag, contained in iron-bearing wastes can be recovered. The feasibility and reliability of this process was investigated thermodynamically and experimentally with the help of HSC 9.0 database and XRD and SEM-EDS analysis. A possible reaction mechanism and path in PbSO4–Fe2O3–Na2CO3–C smelting system was also clarified.

By Zhonglin Ye, Yifeng Shi

"This paper has outlined forms of Au & Ag losses in copper smelting process and methods for increasing Au & Ag recovery, analyzed factors influencing Au & Ag recovery in copper converting process, presented Au & Ag behavior in copper electrorefining process, and reviewed effect of current density/electrolyte circulation rate during electrolysis and surface finish of cathode on Au & Ag losses. Measures and research direction for decreasing Au & Ag losses in electrolysis have also been introduced. Based on Au & Ag behavior in copper electrorefining process and previous studies by others, new approach for increasing Au & Ag recovery in copper smelter has been discussed. And brief comparison has made between continued multiplication method and equilibrium method application in the case of calculation of Au & Ag recovery in copper smelter.IntroductionAs gold and silver are the major by-products from copper smelting process, efficient Au & Ag recovery has become one of the key approaches for copper producers to increase economic efficiency. With similar physicochemical properties, Cu, Au and Ag belong to the first subgroup of elements in the same periodic table. Au and Ag will be enriched into Cu phase firstly when both matte-slag phase and copper-matte phase appear in copper smelting process. However, great changes have taken place in Au & Ag proportions into individual phase due to changes of physicochemical conditions in each smelting process. Metallurgists at home and abroad have carried out a great deal of pilot plant tests and laboratory tests in order to increase Au & Ag the former Soviet Union with regard to Au & Ag losses in copper smelting process in the 1970s and 1980s, and he proposed solutions to increase Au & Ag recovery in copper metallurgical plants. As more than 20 years passed, Jingchun Lu's paper, Discussion on Increasing Au & Ag Recovery in Copper Smelting System, remains as a literature of the most comprehensive study. Based on Jingchun Lu's literature, the authors of this paper discussed new approaches to increase Au & Ag recovery in copper metallurgical plants with combination of many researches done by other researchers for over 20 years."

Jan 1, 2013

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 Onuralp Yücel, Mehmet Bugdayc, Murat Alkan

"In this study, iron based alloys (Fe-Mo, Fe-Cr-Ni, etc.) were produced by using aluminothermic methods starting from Mill Scales obtained continuous casting processes. Mill scales are an oxidised layer of steel alloys containing iron oxide, which includes + 2, + 3 values, on the surface of slabs and billets occurring during annealing in heating furnace at integrated iron and steel milling plant, and continuous casting unit. In the metallothermic experiments, different ratios of starting mixtures and addition of the oxide powders (Alz03, Si02, CaO, MgO) were examined, and their effects on the metal recovery and alloy compositions were carried out. The samples were characterized by using chemical analysis (AAS), XRD, XRF and SEM/EDS techniques.IntroductionSelf Propagating High Temperature Synthesis process (SHS) has many favour compared to the furnace applications, such as low energy requirement, low cost, very short processing time and simple operation, [l, 2]. In a SHS process, the ignition starts the combustion and propagates throughout the reactant mixture yielding the desired product. However, the disadvantages of the process such as inhomogeneous or unreacted products due to undesirable reaction rates needs to be overcome by changing some parameters such as ignition temperature, particle size, additive, atmosphere etc. [3, 4]. Mill scale is a layer of iron oxide which forms on ferrous materials cooling after being processed in hot rolling or continuous casting plants. Mill scale contains iron (II) and iron (III) oxides, which result in a 70% total iron content in oxide form. Not being able to reuse this material will prevent the raw material entering the production plant from being fully utilized [5]. This study aimed to produce Fe-based alloys via SHS (Self Propagating High Temperature Synthesis) metallurgy which is attractive process technique regarding fast and low-cost production ability of cast alloys by using high metallic iron content by reducing continuous casting mill scale."

Jan 1, 2013

By Kimio Itagaki, Makoto Ohtsuka, Kouki Chiba, Minoru Matsumoto

"The properties of Ni-Mn-Ga films such as chemical composition, crystal structure, microstructure and transformation temperature were investigated with respect to sputtering conditions in the present study. The Ni-Mn-Ga films were deposited on a polyvinyl alcohol substrate with a radio-frequency magnetron sputtering apparatus using the NisoMn2sGa2s and Nis2Mn:«1Ga24 targets. After separating from the substrates, the films were annealed at the temperature between 873 and 1273 K for 3.6 ks. The chemical composition of the films depended on the radiofrequency generating power, however, there was no dependence on the heat treatment temperature. Each deposited film had a columnar grain structure. After heat treatment, the width of columnar grains widened and then became indistinct with increasing heat treatment temperature. The Heusler type cubic crystal structure of the fi4n with heat treatment at 1073 K changed to the tetragonal one through the martensitic structural transformation during cooling. The martensitic structural transformation temperature increased with increasing nickel content of films, while the Curie temperature decreased. The film obtained at 200 W using the Nis2Mn24Ga24 target after heat treatment at 1073 K showed one-way shape memory effect through the reverse martensitic structural transformation during heating.IntroductionThe ternary intermetallic compound NiiMnGa has a Heusler-type crystal structure and is an intelligent material, which has a shape memory effect and a ferromagnetic property. The martensitic structural transformation occurs within the ferromagnetic temperature region. The cubic crystal structure of L21 at high temperature changes to a tetragonal one through the martehsitic structural transformation during cooling. The films of this compound can be applied for an actuator of micro-machines."

Jan 1, 2000

By Sharif Jahanshahi

Calcium ferrite slags are often associated with Professor Yazawa due to his pioneering work on the thermodynamics of this type of melts. Over the past years CSIRO has invested some effort in studying physico-chemical properties of such melts to fill in some gaps in our knowledge and explore opportunities for application of the understanding developed. These investigations cover thermodynamics, transport properties of calcium ferrite based slags, as well as the kinetics of reactions of such slags with refractories. The present paper provides an overview of some of these studies and highlights some of the interesting behavior of such melts, The oxidation state of copper and arsenic in calcium ferrite based slags are predominantly Cu+ and As3+, respectively, at oxygen potentials below 10-7 atm. The concentration of CU2+ in such slags becomes significant at oxygen potentials of greater than 10-7 atm at 1300 °C. The activities of CuO0.5 and AsO1.5 in calcium ferrite slags show strong deviations from the Raoultian Law, while that of CoO is very close to ideal behaviour with respect to pure solid CoO. Addition of SiO2 to calcium ferrite slags can have significant effects on the activities of FeO and Fe2O3 and hence the stability of magnetite phase. Transfer of oxygen in calcium ferrite slags is fast with diffusivity of 2x 103 cm2/s at 1350 °C and activation energy of 16 kcal/mol. Presence of solid phases, such as magnetite, has pronounced effect on the viscosity of calcium ferrite slags. The observed dependence on solid loading and shear rate indicates deviation from Newtonian behaviour. The interfacial tension between copper mattes and calcium ferrite slags is strongly dependent on the matte grade, with the determined values being much lower than the corresponding ones for interfacial tension between similar mattes and iron silicate slags. MgO, Cr2O3 and MgCr2O4 have low solubility in calcium ferrite slags and their solubility increases with increasing copper oxide content of the slag at 1300°C. The oxidation state of the slag has strong effects on phase transformation, dissolution rate and disintegration of refractories in calcium ferrite slags. Other key factors with major impact on slag-refractory interactions include viscosity and surface tension of slags as well as the contact angle between slag and refractory material,

Jan 1, 2003

By Z. Zhang, R. G. Reddy

The viscosities of industrial lead slags with various compositions were measured as a function of temperature. It was found that viscosities of lead slags decreased with increasing temperature, and the plots of ln(11) vs. 104tr followed a linear relation over the reported ranges of temperature. Using the data of this study and available other related data from the literature, a viscosity expression was developed as a function of composition and temperature. The calculated results using this viscosity expression are in good agreement with the measured data. The composition dependency of viscosity of lead slags is discussed.

Jan 1, 2000

By N. Kanari

Chalcopyrite concentrates and their pure constituents were chlorinated by C12+N2 between 25 °C and 750 °C. The reaction products were analyzed by SEM, XRD and chemical analysis. The effect of gas flow rate and chlorine content of the gas mixture on the reaction rate were investigated. At room temperature, these solids start to react with chlorine giving metal and sulfur chlorides. Complete reaction is achieved at about 300 °C and the iron and sulfur chlorides were fully volatilized. The chlorination residue is composed of valuable metals&apos; chlorides. A simplified flow - sheet for the treatment of chalcopyrite concentrates by chlorine was suggested.

Jan 1, 1998

By Dachun Liu, Baoqiang Xu, Bin Yang, Yong Deng, Heng Xiong, Xiumin Chen

"In this paper, vacuum distillation technology has been employed to study the possibility and regularity of separating copper and enriching lead, silver and other valuable metals from copper- based multi component alloys. The result of experiment indicated the practicability of vacuum distillation dealing with copper base complex multi-component alloy to separating lead and silver, when the vacuum distillation temperature was 1637K, distillation time was 60min; residual gas pressure was 20-30Pa, the removal rate of silver was 95.86%, of lead was 99.63%; the evaporation rate of copper was 0.745%. The removal rate of arsenic, antimony and tin respectively were 83.09%, 48.12% and 24.54%. Vacuum distillation method is applicable for dealing with the copper-based multi component alloys, silver and lead can realize effective recovery.IntroductionCopper generally go with lead mineral, therefore, to remove copper from lead becomes an inevitable link in lead smelting. Dross from removed copper usually contains lead, arsenic, antimony, tin and noble metal silver. In abroad, soda ash-iron dust is adopted to process copper dross of this kind. The outcomes of this process are lead matte, wet lead, scoria smoke dust etc[1~5] The dominant components of all the outcomes are copper and lead. Moreover, in the process of tin smelting, copper contained by-products are produced, such as, crude tin alloy, tin lead electrolytic anode slime and so on. Copper content of all the products are ranging from few percentages to several tens percentage. Those products, no matter merge into main producing process, or separate treatment cost losses of valuable metal. For one hand, the containing of copper of outcomes from pyrogenic attack is less than 50%, for the other hand, a lot of valuable metal need to be processed, which increase the cost of retrieve."

Jan 1, 2013

By Neng-Wen Yu, Shau-Jun Zhu, Ji-He Wei

The desulfurization process by powder injection and blowing in the RH refining of molten steel and its mechanism have been considered and analyzed. Based on the two-resistance mass transfer theory and the mass balance of sulfur in the system, a kinetic model for the process has been developed. The related parameters of the model, including the mass transfer coefficients and the effective amount of powder in the molten steel being treated for desulfurization, have been more reasonably determined. Modeling and predictions of the process of injecting and blowing the lime-based powder flux under assumed operating modes with the different initial contents of sulfur and amounts of powder injected and blown in a RH degasser of 300 t capacity have been carried out using the model. The relevant circulation rate of the liquid steel and the powder injection and blowing rate were taken to be 100 t/min and 150 kg/min, respectively. The initial contents of sulfur in the liquid steel to be treated and the amounts of powder injection and blowing were respectively assumed to be 0.007, 0.006, 0.005, 0.004, 0.003, 0.002 mass-% and 10, 8, 6, 5, 4, 3 kg/t-steel. The total treatment time for desulfurization under each mode was set up at 24 min, equivalent to eight circulation cycles of the liquid steel to be treated. The results indicated that the predictions made with this model are in good agreement with some data of the industrial experiments and practice. Injecting and blowing the lime-based powder flux with the composition of 85 mass-% lime (CaO) + 15 mass-% fluorspar (CaF2) of 3-5 kg/t-steel, it is possible to decrease the sulfur content in the molten steel to ultralow level below (5-10)x10·4 mass-% from (60-80)x 10·4 mass-%. The total treatment time needed will appropriately be 12-20 min. Intensifying the powder injection and blowing operation and increasing the circulation rate of the liquid steel may effectively' raise the rate of the process in RH refining. The model may be expected to offer some useful information and a reliable basis for determining the reasonable process parameters and help in optimizing the technology of desulfurization by powder injection and blowing in the RH refining of molten steel.

Jan 1, 2000

A modified Cuprex Metal Extraction Process (CMEP) leach process was used to extract Cu. Ni and Co from a complex sulphide concentrate. The standard leach was modified to a two-stage countercurrent leach which provided emf control of the copper SX feed and minimized iron dissolution. A flowsheet was developed to recover the base metals and silver from the leach solution and gold and platinum group metals from the leach residue which was predominantly elemental sulphur. Techniques required to maintain an iron balance in the system including pressure oxidation and solvent extraction are described.

Jan 1, 1996

By J. C. Yannopoulos

The quest for a continuous copper smelting and converting process, which has been going on for a long time, has not as yet reached its objective. The most recent efforts for the development of a continuous copper?making process started about two decades ago. Among the contending proposed processes, four have been piloted and three of them are currently in operation: the WORCRA process., the NORANDA process, the MITSUBISHI process, the OUTOKUMPU process. The WORCRA process, after some long pilot plant tests, failed to develop as an industrial process: The NORANDA process, as currently operating, is a smelting process and not a continuous copper?making reactor as initially conceived. The MITSUBISHI, although the only continuous process, has not been widely accepted. The OUTOKUMPU process can be applied only to a low iron concentrate feed and co?produces blister and high in copper slag. The thermodynamics of these "continuous" systems and the practical problems of their industrial application are reviewed and discussed. The achievement of efficient and inexpensive environmental control should&apos; be the primary objective of any new process development. A review of the environmental problems of the copper industry indicates that the quest for a continuous smelting and converting furnace should be intensified.

Jan 1, 1983

By Isabela Leao Amaral da Silva, Felipe Perisse Duarte Lopes, Alice Barreto Bevitori, Sergio Neves Monteiro

"Jute fibers have in the past decades being investigated as possible reinforcement of polymer composites. However, information is still needed on the fiber interaction with a polymeric matrix for a complete evaluation of the capacity of load transference inside the composite. The present work investigated the interaction of jute fibers with polyester matrix by means of the critical length assessment through pullout tests. Tensile tests of polyester sockets embedded with different fiber lengths allowed the critical length to be determined and then the interface shear stress to be calculated. A relatively low interfacial strength was found, which indicates a weak adhesion between the ramie fiber and the polyester matrix. The SEM analysis of pulled out fibers corroborates this result.Introduction Natural fiber, mainly those lignocellulosic extracted from plants, have, in the past few decades, attracted the attention not only of scientists but also of industrial technologists of our society interested in their engineering applications. As it is well known, uses of natural fiber in clothes carpets, baskets, ropes and low cost construction roofing has existed from the beginning of our civilization. Today environmental and energy saving issues are motivating research works on new uses of lignocellulosic fibers in polymer composites [1-6]. Moreover, industrial application of lignocellulosic fiber composites are already in technological sectors such the automobile industry, packing and civil construction [7-9].In addition to environmental, economical and social benefits, some lignocellulosic fibers present specific properties that are comparable to those of other synthetic fiber used for polymer composite reinforcement. For instance, the specific strength (GPa.cm3/g) of curaua (1.31), sisal (0.92) and ramie (0.93) fibers, from results obtained with very thin diameters [10] are relatively closer to that of glass fiber E (1.33). Therefore, in principle, it would be technically justified to replace glass fiber, which is more expensive, toxic and represents a problem to the environment [ll], by a strong lignocellulosic fiber. However, serious drawbacks such non-uniform dimensions and heterogeneous properties [6] as well as the tendency to form aggregates during processing and incompatibility with a hydrophobic polymer matrix, reduce the potential of lignocellulosic fiber to be used as composite reinforcement [1-6]. In particular, a low interfacial strength causes a weak adhesion between the hydrophilic fiber and the polymer matrix."

Jan 1, 2011

By D. H. Magoon

The zinc smelter of Cominco Ltd. at Trail, B.C. Is the largest In the western world. A total of 550.000 tonnes of concentrate are proceed at the smelter annually. Approximately 80% of the zinc concentrate is roasted and the remainder Is treated by aqueous oxidation preaaure leaching. The zinc concentrate roasting and sulphur dioxide gas processing plants have undergone many changes over the years. This paper describes the processes and equipment currently used for concentrate roasting, S02 gas cooling and cleaning, mercury removal, sulphuric acid production liquid S02 production, and tall gas S02 scrubbing. The recent Installation of an advanced process control system for the operation of these Integrated processes Is also described.

Jan 1, 1990