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By James Vaughan

Ionic liquids are solvents of interest for applications such as electro- plating, winning and refining of metals. Of particular interest is the possibility of processing reactive metals such as aluminium, magnesium and titanium that cannot be deposited from aqueous solutions. Aluminium has been electro deposited from AlCl3 : ionic liquid mixtures at low temperatures relative to conventional Hall-Héroult smelting. Imidazolium ionic liquids are have been used in the past due to their relatively high ionic conductivity and cation stability. The less studied and less expensive phosphonium ionic liquids systems may provide a viable alternative to imidazolium ionic liquids for certain applications. New information regarding the physical properties and electrochemical behaviour of phosphonium ionic liquid systems is presented.

Jan 1, 2006

By T. Feldmann

Despite the ubiquity of applications for germanium, there is a lack of practically useful solubility data in acidic solutions. Previous studies were done at ambient temperature and only for commonly used acids (H2SO4, HCl). Hence, an investigation of the solubility of GeO2 in different acids was undertaken. Several inorganic and organic acids were studied in the concentration range of 1–11 mol/L and at 23, 40, and 60 °C. In the case of H2SO4 and HCl previous data was confirmed. Lower acidity resulted in a higher solubility for Ge at all tested temperatures. Tests done at 40 and 60 °C and low to moderate acidity levels, gave slightly increased solubility values at higher temperatures compared to 23 °C. This wasn’t the case at higher acidity levels, i.e., the solubility curves at different temperatures converge at high acidity. Lastly, a relationship of water activity and GeO2 solubility in different acid media was established.

By Yasushi Sawada

An experimental investigation was carried out to study the rates of reduction of iron oxides dissolved in liquid Ca0-SO2-A203 slags by Fe-C droplets at temperatures ranging from 1325 OC to 1550 OC. The %FeO in the slag was varied from 5.5 to 18. Flash X-ray images were employed to observe the behavior of Fe-C droplets in the slags during the reactions and for determining the slag-gas-metal interfacial area. Effect of P205 in the slag and sulfur in the droplet was also investigated. The reduction rates were determined by measuring the volume of CO evolved as a function of time and the estimated slag-gas- metal interfacial area. The reduction rates have increased with increasing %FeO in the slag and the slag temperature. The experimentally established relationship between the reduction rates and FeO (wt%) in slag is given by

Jan 1, 1992

Steel Ladle in Bhilai Steel Plant, SAIL, India, passes through VAD & LF-RH route and this exposes refractory lining to a severe operating conditions. Ladles are lined with in-house manufactured MgO-C refractories. Lining life used to be 35 heats, out of which 18-20 heats were through VAD/LF-RH, hence, ladle availability had become a constraint. Laboratory studies were carried-out to optimize granulometry and composition. Granulometry was developed by adopting Andearssen packing model. A suitable plasiticiser was identified to eliminate inconsistency caused due to variation in resin quality and weather condition. It reduced variation in green bulk density from 6 to 1.3%. Abrasion and slag erosion studies were conducted, which shows that with increase of carbon, abrasion resistance decreases and corrosion resistance improves. Based on these studies, graphite in slag zone was increased from 10 to 12.5% and in metal zone it was reduced to 7.5%. Different process parameters of brick making were optimized to make MgO-C bricks of maximum bulk density with reduced coke porosity. Modified bricks have bulk density of 2.99-3.02 g/cc and coke porosity of 9.5-10.5%. Further, shape of the bricks were changed from side arch to mini keys and thickness was increased from 80 to 100 mm. Mini key bricks are pressed from sides, thus eliminating variation in thickness which is critical dimension for dry joints. These modifications improved average lining life of steel ladles to 64 heats, which includes 37-40 secondary heats. Maximum life obtained is 87 heats.

Jan 1, 2006

By Seyed Mahdi Abbasi, Adel Sheikhhosseini

"This research was conducted to study the changes of microstructure, chemical composition and mechanical properties ofIN718 superalloy after adding aluminum to the ESR process slag. The experiments were performed in VIM and ESR furnaces. The results showed adding 1.5 percent aluminum to the slag increase lave phase in the IN718 samples from 0.34 percent in the base sample to 3.0 percent. It also indicated that the more increase of aluminum in slag cause decrease in the aluminum absorb yield in the superalloy.it is observed that increasing aluminum from 0.7 to 1.1 and then to 1.5 percent caused a decrease of absorb from 91.4 to 76.3 and 74.6 percent respectively due to increasing of aluminum oxidation. According to the results, tensile strength increased and ductility declined in the IN718 samples mainly because of rising the amount of y' volume fraction.IntroductionIN718 superalloy is an iron-nickel base superalloy with constant mechanical properties at medium at high temperatures. For the past seven years a considerable amount of time and effort has been expended by both suppliers and users in the study of Alloy 718 [ 1]. The interest in this material stems not only from the interesting metallurgy associated with the alloy, but with the large usage of the material in numerous applications In fact many people believe that the projected use of this alloy increase significantly over the next several years, The large use of Alloy 718 is the result of its performance in respect to high strength, good ductility, good repair weld ability and from its versatility of being supplied in various product forms. This superalloy is used in wide ranges of industries such as aerospace and gas turbines [2]. In the past more than 20 years many researchers did a lot of work to improve the structure stability of IN718 at high temperatures and intended to develop a new 718 type alloy to be used beyond 650 °C. One of the methods is to control and phase precipitation behavior by means of adjustment of Al, Ti and Nb contents. The other idea is to strengthen the matrix by altering the content of solid solution elements such as W and Co. The adjustment of these alloying elements can change phase precipitation behavior [3]. If detailed information dealing with phase precipitation behavior can be obtained before experimental work for alloy development, a lot of time can be saved and the development cost can also be reduced. In recent years, computer modeling based on experimental data plays an increasing role in alloy design and development. Adding Al to the Iron and Nickel increas the strength of superalloy by formation of y phase and subsequence formation of n phase. Ti in IN718 superalloy also helps the formation of MC carbides and gamma prime phase. Increasing Al/Ti and (Al + Ti)/Nb will lead to form finer particles of y'. More uniform distribution of the precipitates and enhancing stability of y' in IN718 superalloy [ 4]. Adding Al to slag of ESR process can reduce the oxide inclusions because of the strong tendency of Al to oxidation. In addition, tensile properties of IN718 superalloy improve. The most significant inclusions in IN718 superalloy are Alz03 and TiN that were found in agglomerate forms. Thermodynamic calculation results indicate that the effect of increasing Al shows a strong increase in solvus while phase solvus shows mildly decrease when Al level is less than 2%, after that it dramatically decreases [ 5]. Laves phase precipitation and the appearance of phase are occurred when Al content reaches 2%. In fact, when Al content is beyond 1.5%, phase has already precipitated in a considerable scale. Shows the fraction of increases greatly while the fraction of phase decreases remarkably with the increment of Al content. Based on thermodynamic theory, if these particles were not existed in the melt during cooling agglomeration would not accrue and the superalloy will be cleaned By adding Aluminum to the slag, the metal reacts with oxyge"

Jan 1, 2013

By S. G. Kumar, R. G. Reddy

"Niobium aluminides offer the advantage of higher high temperature capability compared to other intermetallic aluminides due to the refractory nature of niobium. However, the reaction sequence in Nb-Al system is sluggish and currently there is a great interest in the processing aspects of these materials. In the present study, a systematic investigation was undertaken to compare the effect of different powder metallurgy processing routes on the phase relations and microstructure of 66Nb-22AH2Ti (in atom percent) alloy. The three different process routes adopted were: (i) cold pressing followed by reaction sintering; (ii) cold pressing and hot pressing followed by sintering; and (iii) arc melting, hydride-dehydride process to make the alloy powder followed by cold pressing and then sintering. The samples are analyzed by XRD, Optical Microscopy, SEM-EDS and EPMA. The analysis showed that alloy pellets made from pre-alloyed powders i.e., arc melting followed by hydride-dehydride process, gave good densification and more Nb3Al formation.1. IntroductionTo improve the performance standards of turbine engines, materials scientists are challenged to develop materials that have· high thrust-to-weight ratio with high specific strength, high specific modulus and good environmental properties at elevated temperatures. The conventional high temperature materials like nickel based superalloys are high in density and hence many of the high temperature materials scientists have focussed their attention on intermetallic aluminides like Fe-AI, Nb-AI, Ni-AI and Ti-AI in recent years. The phase relations and properties of alloys based on Fe-AI, Ni-AI and Ti-AI are fairly well known whereas little is known about the alloys based on niobium aluminides."

Jan 1, 1996

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 Petre Stelian Nita

In small steelmaking shops, in foundries and forging plants, there are not too many option to recycle the basic slags, which are not suitable for many purposes of recycling, because of their low chemical and structural stability. A solution of an adequate recycling is a direct recycling in EAF. Several quality requirements, physico-chemical properties and proportions of slags must be analysed. The progress in this fields permites to establish an adequate proportion of recycled slag, based on enough exact computation of the related property. For oxydizing slag, obtained during melting and in the first part of decarburization operation, the problem of phosphoms contents can be analysed using the phosphate capacity (C PO34-). For reducing periods, during deoxidization operation, desulphurization also occurs and the problem of the sulphur contents can be analysed using the sulphur and sulphide capacities ( Cs / Cs) Between this two complex thermodynamic indicators of the slags. a direct relation is established, using thermodynamic aspects, resulting from the equilibrium constants for dephosphorization and desulphurization process and also, using the optical basicity of slags, computable from the chemical analysis of the slags. On this basis starting from the steel quality requirements. adequate strategies can be established in order to obtain high rates of recycling (between 50-80%) of steelmaking slags. Important cost savings are obtained through this procedure, based on the correct amounts of the fresh lime, iron ore and fluidizers. Keywords: Slag, Properties, Recycling

Jan 1, 2003

By Markus A. Reuter, Jacob Wood, Robert Matusewicz

Over the last 20 years, significant improvements in copper smelter productivity have been realized through the advent of continuous smelting processes. This progress has until recently however, not been carried through to copper converting. Peirce-Smith converting has been widely used by the copper industry for 100 years but is limited by its batch nature in achieving large scale of production. A logical next step is therefore copper converting on a continuous basis with its inherent environmental benefits. A number of continuous converting technologies are currently in use or being developed within the copper industry, the majority of these operating with calcium-ferrite slags. A notable exception however is the Ausmelt Continuous Copper Converting (C3) technology which has focused on operation with ferrous-calciumsilicate or loosely called olivine type slags. This paper discusses the merits of the Ausmelt C3 process and the advantages offered in terms of operational flexibility and process control arising from the use of lime modified iron silicate slags. It also examines the effects of key process variables pertinent to continuous copper converting from both a theoretical and experimental/operational perspective.

Jan 1, 2009

By Akira Yazawa

The continuous converting has attractive advantages, but further experimental studies on the slag are required, when the process is considered thermodynamically. The summarized experimental results, obtained with iron silicate slag and with ferrite slag and results relating to actual operation are described and discussed in this paper. At first, equilibrium relations at controlled oxygen potentials among three melts of silica-saturated iron silicate slag, white metal and copper are investigated. The results obtained for slag agreed with the thermo-dynamical predictions. Namely, to suppress a magnetite separation, the system should be at high temperature; in the case of the S02 gas of 10 kPa, for example, magnetite did not separate from the slag at 1300°C, but at 1250 and 1200°C the slag was saturated with magnetite even at lower SO2 pressure. Copper losses caused by dissolution of its oxide increased with increasing 5O2 pressure, and were slightly lower than those reported in previous papers without the matte phase. When the continuous converting slag does not contain any appreciable amount of silica - in contrast to the conventional smelting slag ferrite slag would form, but there was no published fundamental work on-ferrite slags. Hence, the melting behavior and activities of the system CaO-Cu2O-Fe2O3 have been investigated. The liquidus diagram in nitrogen atmosphere was, constructed using both thermal analysis and quenching method. The low liquidus temperature region without magnetite separation was found in the part of low content of Cu2O in the section Cu2O-CaO-Fe2O3 and Cu2O?Fe2O3¬CaO?Fe2O3. The activity of Cu2O in the system was also measured. Slags, composed-of CaO, Cu2O and Fe2O3, in platinum crucibles were equilibrated at 1250°C and controlled oxygen pressures. After quenching, the-composition of slag and platinum crucible were determined qualitatively. On the thermo-dynamic analysis of the results, iso-activity lines were drawn, and it was shown that the slag in the converting furnace of the Mitsubishi process exists in an adequate region of the composition triangle.

Jan 1, 1976

By Y. Takasaki

For zinc hydrometallurgical extraction, reducing the electric power consumption of the electrowinning process is an important issue for energy savings. At the Zinc & Lead 2000 symposium, the authors suggested that by using the Pb-0.5%Ag-0.6%Ca alloy, the electrolysis energy can be decreased compared to the conventional Pb-0.9%Ag alloy. In this study, the corrosion behaviors of the Pb-Ag-Ca electrode in a sulfuric-acid electrolyte were investigated. Based on the results Or me Pb-0.5%Ag-0.6%Ca anode after 20 days of electrolysis, the bath voltage and the quantity of anode slime decreased compared to the Pb-I%Ag anode. Subsequently, beta-PbO2 on the electrode surface was detected by XRD and its peaks were sharper than the Pb-1 %Ag anode. Moreover, a dense beta-PbO2 layer on the 0.6%Ca a anode surface was observed. Therefore, it was suggested that the dense beta-PbO2 layer on the anode surface is one of the factors that leads to a lower bath voltage and decreasing quantity of anode slime.

Jan 1, 2003

By Zhigang Zak Fang, Michael L. Free, Jaehun Cho, Syamantak Roy, Amarchand Sathyapalan

Leaching characteristics of impurity removal from the Upgraded Titania Slag (UGS) using hydrochloric and boric acids has been investigated. Specifically, this study has focused on removal of iron oxides from the UGS that has been reduced by hydrogen gas and magnesium at 750oC for 5 hours. Reduced UGS is mainly composed of titanium hydride and impurities like iron oxides, silicon oxide, aluminum oxide, and magnesium oxide. The concentration of hydrochloric and boric acids and the leaching temperature have been chosen as the prime variables to identify the optimum conditions and leaching characteristics for removal of iron oxides. It was observed that under the constraint that 1 wt % of titanium hydride loss is the maximum amount tolerable, 0.1M HCl with 1M boric acid and 90oC are the most effective parameters for iron removal from the reduced UGS. Also, the overall rate of reaction seems to follow interfacial reaction controlled kinetics. The calculated activation energy of the reaction is 73.90kJ/mol.

Jan 1, 2016

By C. M. Diaz

The chemistry of the main unit processes in nickel extractive pyrometallurgy is reviewed. Key re1a ions between smelter feed composition and process selection are discussed, with particular reference to operating conditions, energy requirements and products. The paper a1 so includes a brief discussion of current nickel smelters, based on the results of a recent survey carried out by TMS.

Jan 1, 1988

By Katsuyoshi Kondoh

The synthesis processing of Mg2Si or Mg2Si/MgO at lower temperature from the elemental magnesium alloy powder/chips and Si or SiO2 powder mixture was established via the repeated plastic working (RPW) based on Powder Metallurgy (P/M) process. RPW is much effective on the mechanical breakage of MgO surface films, which prevent from the solid-state reaction between Mg and Si powder. The solid-state synthesized Mg2Si particle of 200nm-2JIm is extremely fine, compared to that via the conventional casting process, causing the coarse one of 50-100um. This is because of not coarsening during the solid-state synthesis of Mg2Si. By using in-situ forming process of Mg2Si via RPW and pre-heating before hot working such as extrusion and forging, the magnesium composite material with Mg2Si or Mg2Si/MgO dispersions was developed in employing Si or SiO2 particles, respectively. For example, when employing AZ31 chips as raw materials of the matrix, it has low density of 1.85g/cm) and extremely superior mechanical properties, such as tensile strength over 350MPa with 5-10% elongation and Young's modulus of 47-50GPa, to the conventional Mg-Al-Zn alloys. The Mg composite alloy wires and pipes were produced via the hot extrusion process in the manufacturing plant, and also showed excellent mechanical properties.

Jan 1, 2003

By John T. Berry, Robert D. Pehlke, Michael J. Beffel

"Pattern making and metal casting organizations are currently adopting CAD/CAM systems and implementing this technology in design and production. Al though significant progress has been reported, these systems generally are based on two or two and one half dimensional analyses. Very few are based on solid geometric modelers.The present paper emphasizes the need for solid geometric modeling of the casting and rigging system and linkage with a solidification simulator. The nature of some of the technological challenges which have slowed this development are discussed, including accurate description of complex surfaces and their intersections and the bridging of computer encoded information with NC technologies and with FEM-based simulators for stress and thermal analyses. A recently prepared modular-structured FEM simulation code implemented on a micro computer is described.Construction of a solid geometric model of the casting and rigging and validation of the combination for optimum characteristics of soundness, quality and yield by solidification simulation are I inked as key elements in the foundry of the future. Data base support for this CAD/CAM system is rapidly being developed throughout the world.INTRODUCTIONThe simulation of shaped casting solidification using the digital computer, goes back to at least the early nineteen-sixties when Forsund (1) in Denmark applied the technique to the problems of casting surface quality.Prior to that time, the work of Paschkis and co-workers using the analog computer ranges back to the nineteen-forties, when work sponsored by the AFS Heat Transfer Committee at Columbia University revealed many hitherto unknown or only partly anticipated aspects of casting solidification (2).Three reviews of the various historical aspects of simulation should be referenced. Firstly, the AFS monograph by one of the present writers (RDP) and his colleagues - describing background and later work, again sponsored by the AFS Heat Transfer Committee at the University of Michigan (3). Secondly, a review prepared by Durham and Berry (4) which discusses broad aspects of casting solidification simulation. Thirdly, a review by Erickson (5) which contains an excellent bibliography to 1980. In addition to these papers, the publications lists of the CADCAST project* and the proceedings of the two Engineering Foundation Conferences of Casting and Welding Modeling, published by ASME, are also most notable (6) •"

Jan 1, 1986

By Katsuyoshi Kondoh

The synthesis processing of Mg2Si or Mg2SiIMgO at lower temperature from the elemental magnesium alloy powder/chips and Si or SiO2 powder mixture was established via the repeated plastic working (RPW) based on Powder Metallurgy (PIM) process. RPW is much effective on the mechanical breakage of MgO surface films, which prevent from the solid-state reaction between Mg and Si powder. The solid-state synthesized Mg2Si particle of 200nm-2um is extremely fine, compared to that via the conventional casting process, causing the coarse one of 50-100um. This is because of not coarsening during the solid-state synthesis of Mg2Si. By using in-situ fonning process of Mg2Si via RPW and pre-heating before hot working such as extrusion and forging, the magnesium composite material with Mg2Si or Mg2Si/MgO dispersions was developed in employing Si or SiO2 particles, respectively. For example, when employing AZ31 chips as raw materials of the matrix, it has low density of 1.85g/cm3 and extremely superior mechanical properties, such as tensile strength over 350MPa with 5-10% elongation and Young's modulus of 47-50GPa, to the conventional Mg-Al-Zn alloys. The Mg composite alloy wires and pipes were produced via the hot extrusion process in the manufacturing plant, and also showed excellent mechanical properties.

Jan 1, 2003

By Daniel Kim, Ari Rantala

Efficient on-line monitoring of electrolytic cell performance in copper electro-refining has been challenging due to the need for complex electrical measurement systems and the management of the enormous volume of data. Based on Kennecott Utah Copper's innovation Outotec has developed a novel and innovative electrolytic cell monitoring system called CellSense™ System. As the system is based on self-powering from bus bars, wireless communication, on-line adaptive modeling and easy to access information and alarming, traditional obstacles of electrolytic cell monitoring are eliminated. With cell voltage and electrolyte temperature measurements, CellSense System enables real-time cell performance discovery and early reaction to critical production or quality disturbances such as short-circuiting, flow blockages, cold cathodes or electrolyte temperature excursions. During the past few years the system has been delivered to over 3500 commercial cells. In this paper the largest CellSense™ System ever delivered and recently adapted by Kennecott Utah Copper with 1412 cells monitored on-line for high tankhouse performance, cathode quality and optimized operator work flow is presented. Early results and benefits are discussed.

Jan 1, 2012

By Li Fangi

This paper describes the characteristics and regularities of a process to recover rare earth minerals from Baotou Ore with H-205 collector. H-205 is a kind of hydroxamic acid with amide as a polar group and poly-cycle aromatic hydrocarbon as a non-polar group, having strong ability to capture RE minerals (bastnasite, monazite). When adding a certain dosage of water glass and some other modifying agents, and maintaining pH value between 8.5 and 9.5, RE minerals can be effectively separated from calcium and barium minerals, such as fluorite and barite, etc. Under normal flotation temperature and concentration, when using H-205 to float RE minerals, it needs a bit longer conditioning time (a few minutes longer than that for the conventional collectors). It is also shown that the reagent has the property of resistance to hard water. The laboratory scale and pilot scale tests of the process have been carried out on bulk froth containing RE minerals and fluorite taken from Ore Dressing Plant of Baotou Iron and Steel Company, in both cases, high grade RE concentrates were obtained and the recovery increased remarkably. Therefore, the process has a great practical value.

Jan 1, 1989

By Stober, Frank Allan

The paper describes the development of components in an lntegrated Furnace Control system for shielded-arc smelting focusing on operation and crucible integrity enhancement. The paper reviews the mechanisms of power, feed and energy input and losses into the shielded-arc smelting process and describes the furnace control system module development and integration to tailor the process. The ultimate success of a furnace control system application is transfer of knowledge, training, and operational support during furnace start-up and ramp-up phases and a model for how this has been achieved is discussed. The control modules of a shielded-arc laterite smelting furnace are described in detail including measured results and screen captures from application in a laterite smelting furnace. This paper focuses on developments in Integrated Furnace Controls tailored to shielded-arc laterite smelting but development of common furnace control modules for improved crucible and tapping operation integrity applied to other furnace processes, including immersed-arc smelting, is also covered. Keywords: IFC, Power, Feed, Supervisory, Control

Jan 1, 2004

By S. Yabe

The reinforcement of the annual copper production capacity to 330,000 metric tons has been attained at Saganoseki Smelter & Refinery in 1991, which is one of the largest and most efficient custom smelters in the world. Many operational improvements and technology developments have realized the increase of smelting and refining capacity without adding main facilities to the existing process. The blister copper refining and anode casting process is composed of two 400 tonnes anode furnaces and one double-wheeled casting machine with the capacity of 80 tonnes per hour. The great innovations in this process such as the finding of essential issue on the extending of anode-mould life and the development of a new anode-mould casting machine have raised the operation efficiency by 14% Now, the process is producing 38,500 tonnes per month of best quality anode in well- controlled working condition, and anode productivity per worker increased by 52%. The progress in extending anode-mould life, the mechanism of the new anode-mould casting machine and the increase of efficiency in butane reduction, that were the principal parts of many technological improvements, are described in the present paper, including some operation results.

Jan 1, 1993