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By Miroslav Raudensky, Kallol Bera, Jaroslav Horsky, Jee G. Chang, Ampere A. Tseng

"A combined experimental and finite element approach to study the local heat transfer coefficient is presented in this paper. The heat transfer coefficients at different cooling regimes in a roll are quantified by an inverse heat conduction technique; the heat transfer phenomena involved are then discussed. A discussion of the application of the heat transfer information found in the present study for better design of a roll cooling system is also included. Finally, an identification of areas where further work is needed is presented.IntroductionIn metal rolling processes, the roll is used as a tool to deform the workpiece at very high speeds. As shown in Fig. 1, the heat transfer phenomena involved in the process are complicated by the interaction between the roll and the strip, mainly including 1) the heat transferred from the workpiece to rolls in the contact regions, 2) the heat created in the interface due to the deformation of the workpiece and the friction between the workpiece and roll, and 3) the heat removed by watercooling as well as the ambient air. All of these transport phenomena occur at extremely high pressure, high speed, and high heat flux; these make the control of the roll temperatures an extremely challenging problem.In hot rolling, proper cooling of rolls can lead not only to improve the roll shape quality by controlling the thermal crown of the roll, but also to extend the roll life by minimizing the thermally induced stresses [1,2]. Also, knowledge of roll temperatures can contribute to insights about the roll/workpiece interfacellubricant behavior, and lead to the desired surface condition of the workpiece. Therefore, adequate roll cooling or control of roll temperatures is of critical concern to mill designers and process engineers. In order to have proper operation of the process, a good understanding of the influence of cooling practices on the roll is essential [3]."

Jan 1, 1994

By Peter V. Barr

Despite the advent of modem firing control systems reheating furnace operations frequently allow significant thermal excursions in the discharged slabs or billets after furnace delays. Although HSM furnaces are not immune to this and other related problems, mini-mill operations are most vulnerable due to their more frequent delays and (often) less sophisticated control systems. In order to reduce these problems control systems will commonly include a thermal model, operating either on-line (interacting directly with the controller logic) or in an advisory, off-line mode. Using a new 'fast' thermal model, the paper examines the thermal response of a typical mini-mill furnace during both delays and the subsequent recovery period. A variety of firing strategies are explored and compared on the basis of maintaining thermal excursions within allowable limits for rolling. Other factors, such as the potential for overheating of billets within the furnace during delays and the overall thermal state of the furnace, are also considered in some detail. Although common practice, the use of conventional thermocouple zone temperatures for furnace control during and after delays is shown to be a dubious proposition. Keywords: Reheat Furnace, Modeling, Process Control

Jan 1, 2003

By Wenxian Zhu, Xuema Li, Patrick R. Taylor

"Experiments were performed in a non-transferred arc, thermal plasma flow reactor to investigate the synthesis of ultra fine boron nitride (BN) powder from the reaction system of boron oxide (Bz03), methane (CH4), ammonia (NH3) and hydrogen (H2). Argon (Ar) and nitrogen (N2) were used as plasma gases. The thermodynamics and kinetics of the synthesis reactions were examined and a chemical reaction mechanism was proposed. The powders produced under certain operating conditions had high purity and good conversions. All the products were extremely fine powders (< 30nm) and were uniform in size distribution. The powder products were analyzed by chemical and physical characterization. The effects of the reaction variables on the conversions from B203 to BN and the purity of the products were investigated.IntroductionIn the past few decades, boron nitride (BN) has attracted a great deal of interest because of its excellent thermal, chemical and electrical properties (1-4) It has a high thermal stability and thermal conductivity. Chemically, it is very stable and is not wetted by most molten metals and slag. It is also an excellent low loss insulator. Since hexagonal boron nitride (h-BN) is light in weight, strong and easily fabricated, it has applications in a variety of specialized high temperature areas, such as a high temperature lubricant, crucibles for molten metals, thermocouple protection tubes, break rings for horizontal continuous casting of steel, and friction reducing coatings. In cubic form, boron nitride is one of the hardest materials known, second only to diamond, and it is an excellent material for tools in which the use of carbon based materials is limited by oxidation or reaction with metals."

Jan 1, 1998

By Matthew C. Binsfield

The simultaneous electro winning of zinc and manganese from waste water treatment plant sludge was studied as a part of the overall research program, which was conducted to develop the methods for removal of environmentally hazardous metals from the Bunker Hill Superfund Site. This paper discusses the electrolytic method for recovery of zinc and manganese from the solution produced by leaching of sludge with S02 + H2S04. After three stage purification of the leaching solution, zinc and manganese were electro won simultaneously in an undivided electrolytic cell. Zinc was deposited on an aluminum cathode, while manganese was simultaneously produced (as Mn02) on a lead silver anode. The electrowinning parameters studied were the effects of: temperature, current density, electrode material, spacing of electrodes, composition of electrolyte, and electrolyte additives. Anodic and cathodic efficiencies were 30 and 91%, respectively. In light of the process design parameters discussed in the paper, which are affecting the electrowinning, these efficiencies were found as acceptable with regard to the quality and marketability of the products.

Jan 1, 1996

By H. Y. Sohn, S. PalDey

"Fine particles of nickel aluminides and Ni4Mo were synthesized by reducing mixtures of, respectively, A1Cl3 + NiC12 and NiC12 + MoC12 vapors with hydrogen. Though thermodynamically favorable, the coreduction of NiC12 and A1Cl3 by H2 to form Ni3Al did not readily happen experimentally. The addition of a small amount of aluminum vapor was needed to initiate the coreduction reaction. The product particles as observed by TEM were very fine but usually agglomerated. The electron diffraction pattern of particles identified NiAl and NiA13 along with Ni3Al and metallic Ni. The content of Ni3Al was maximized at 52 mol% at 1050°C under the partial pressures ofH2, A1Cl3, and NiC12 at 57, 1.4, and 0.5 kPa, respectively. When a mixture of NiC12 + MoC15 was reduced by hydrogen, Ni4Mo particles with some Ni or Mo particles were obtained, the maximum content of Ni4Mo obtained being 93 mol % . The particle size was in the range of 100 to 200 nm. An Ni4Mo coating of 700 nm thickness on an Ni substrate was also prepared.IntroductionThe search for new high-temperature structural materials has stimulated much research on intermetallic compounds. Nickel aluminides have low densities, relatively high melting points, and good high-temperature strength properties. They show an increase, rather than a decrease, in yield strength with increasing temperature (1). Ni4Mo is also of interest as a high-temperature structural material. The major shortcomings of these intermetallics are their inherent brittleness at room temperature when they are in polycrystalline form. For much the same reason, the conventional casting of intermetallics is difficult. Ingot metallurgy and powder metallurgy are two other processing techniques. The first technique is quite energy consuming. In powder metallurgy, the powders of metals and alloys are consolidated in near net shape and then subjected to secondary processing. It would, therefore, be advantageous if intermetallic compounds can be produced in fine powder form from inexpensive raw materials, using less energy."

Jan 1, 1998

By G. Cifuentes

The kinetics of the electrolytic oxidation of cyanide to cyanate on PbO2-coated stainless steel anodes have been studied by both experimental and theoretical means. The anodes were based on 316 steel and performed in a satisfactory fashion. The pH of the studied KCN solutions exhibited a constant value about 11. Values for all the kinetic parameters have been determined and a mechanism for the studied reaction is proposed.

Jan 1, 1999

By Yimin Ruan

"An inverse design method is developed to obtain the optimal cooling conditions for the continuous quenching of precipitation hardenable sheet alloys to achieve the required yield strength. The yield strength of a precipitation hardenable alloy is obtained by allowing solute to enter into solid solution at a proper temperature and rapidly cooling the alloy to retain the solute in the solid solution. An aging process may be needed for the alloy to develop the final mechanical properties.The objective of the design is to optimize the quenching process so that the required yield strength can be achieved. With the inverse design method, the required yield strength is specified and the sheet thermal profile at the exit of the quenching chamber can also be specified. The conjugate gradient method is used to optimize the cooling boundary condition during quenching. The adjoint system is developed to compute the gradient of the objective functional. An aluminum sheet quenching problem is presented to demonstrate feasibility of the inverse design method.IntroductionQuenching is a critical step in metal production to achieve desired material properties, such as yield strength, hardness, etc., for precipitation hardenable alloys. In most cases, rapid quenching from the solution heat treatment temperature is necessary to obtain the required material properties, but rapid quenching may cause other problems such as excessive distortions of the quenched materials.In a solution heat treatment, the alloy is heated to a suitable temperature, held at that temperature to allow the soluble alloying elements to enter into the solid solution, and cooled rapidly (quenching) to retain the alloy elements in the solid solution. An aging process, which controls precipitation of fine particles at room (natural aging) or elevated temperatures (artificial aging), is generally followed after the quenching process to develop the final mechanical properties of the heat treated alloys."

Jan 1, 1998

By C. D. Mishra

The recycling potential for any gainful utilisation of the waste products is dictated by their quality, especially the chemical characterisation. The methods commonly used for the analysis of fly ash e.g. wet chemical, AAS, ICP-AES etc are time consuming. The paper describes a rapid XRF-based method for routine analysis of fly ash which involves preparation of local standards, optimisation of sample preparation technique and use of a simple PC-based software to account for interelement effects. The matrix corrected values are found to agree well with the wet chemical data.

Jan 1, 1992

By Bin Xu, Qian Li, Yong-bin Yang, Tao Jiang, Jian-jun Hu

It could significantly increase the leaching rate of refractory gold concentrate containing sulfur and arsenic by roasting pretreatment with adding certain amount of sodium sulfate, and the mechanism of that was systematically researched with DSC, XRD and SEM in this paper. Results indicated that the mechanism of Na2SO4 on double refractory gold concentrate at roasting pretreatment can be summed up in the following three aspects：Firstly, Na2SO4 can react with SO2 and SO3 which is produced by the oxidation of sulfides and generate Na2S2O7(l), which plays buffer effect on sulfides exothermic oxidation, avoiding the secondary-encapsulated of gold. Secondly, the liquid phase of Na2S2O7 can cover mineral particles' surface that possesses a sintering effect, it leads to internal cracks of the particles. Finally, mineral particles will gather with sodium sulfate particles as the center that can improve the permeability of the layer.

Jan 1, 2015

By Wenjun Duan, Kun Wang, Qingbo Yu, Qin Qin

"A novel oxygen production technology noted chemical looping air separation (CLAS) was introduced and properties of Cu-based oxygen carriers used were investigated. The oxygen carriers were prepared by mechanical mixing. Al2O3, Fe2O3, ZrO2, TiO2 and SiO2 were used as binders during the preparation. XRD patterns show that spine! oxides are formed using Al2O3 and Fe2O3 as binders. Phases of CuO and binders keep stable using ZrO2, TiO2 and SiO2 as binders. BET values of oxygen carriers increase in the order of ZrO2>TiO2>SiO2>Fe2O3>Al2O3. The effects of temperatures, binders, particle sizes and flow rates on reduction/oxidation reaction rates were studied in TG experiments. The reduction reaction rate increases in the order of ZrO2>TiO2>SiO2. The effect of binders on the reactivity of oxidation is not obvious. The reduction and oxidation reaction rates both have the tendencies of increasing with the temperature increasing and with gas flow decreasing. However, the effects of gas flow and particle size are little.IntroductionChemical looping air separation (CLAS) is a novel oxygen production technology. The oxygen carriers used in CLAS release oxygen in reduction reactor and regenerate in the oxidation reactor. Selecting suitable oxygen carriers is the key for CLAS. Oxides of CuO, Mn2O3, Co3O4, Pb3O4, CrO2, SrO2, PdO2 and CeO2 have the property of releasing oxygen at suitable temperature and oxygen partial pressure [1]. Among these oxides, CuO, Mn2O3, Co3O4 are the most common compositions used to prepared oxygen carriers for chemical looping combustion (CLC) or chemical looping with oxygen uncoupling (CLOU) [2-5]. Moreover, thermodynamic calculations and preliminary experiments were carried out on oxides of Cu (CuO/Cu2O), Mn (Mn2O3/Mn3O4) and Co (Co3OJCoO) by Moghtaderi to ascertain their feasibility for CLAS process [6]. CuO has the highest oxygen transport capacity (0.1 g 02/g CuO compared to 0.03 g 02/g Mn2O3 and 0.06 g 02/g Co3O4). However, agglomeration is the biggest issue for copper oxides used at high temperature because of its low melting point (l 450°C for CuO, 1235°C for Cu2O and 1075°C for the mixture of CuO and Cu2O) [7]. In order to improve the capability of anti-sintering and stability ofCuO, binders (ZrO2, MgAl2O4, TiO2, SiO2, Fe2O3, Al2O3, cement) are added during the preparation of Cu-based oxygen carriers [8]. In this paper, the Cu-based oxygen carriers were prepared by mechanical mixing method. TiO2, Al2O3, Fe2O3, ZrO2 and SiO2 were selected as binder. XRD, BET and SEM were used to analyze the phase, surface area and surface morphology of oxygen carrier prepared. The reactivity of oxygen reduction and oxidation of oxygen carriers prepared were investigated in STA409PC thermal analyzer."

Jan 1, 2014

By D. E. Roberts

Over 425 million used automotive oil filters are discarded in the United States each year. Estimates prior to this research claim that 10% are recycled with the remainder typically being landfillcd. Surveys conducted with ferrous scrap users and oil filter processors as part of this research reveal that at least 15% are currently being recycled as ferrous scrap. Oil filter scrap is not being used by many operations because of concerns with scrap consistency and quality. These concerns stem from trials conducted in the infancy of the oil filter recycling movement. Consistent scrap quality depends both on the content of the used oil filters and the processing technique used to produce the scrap. Technology has advanced since the first recycling trials were conducted by steelmakers. Several different types of scrap are available, including pucks, bricks, cubes, and shred. This research conducted at the University of Missouri-Rolla investigated the content of used oil filters and compares the recyclability of different oil filter sizes and designs. Filters vary by application and vary between manufacturers for a particular application. An understanding of the scrap itself as well as the concerns and problems of both oil filter recyclers and oil filter processors is necessary to increase the number of used oil filters being recycled.

Jan 1, 1996

By Bowen Li, Matthew D. Andriese, Jiann-Yang Hwang, Zhiwei Peng

"Magnetic iron sulfide ore particles heat rapidly by microwave (MW) irradiation generating plasma during oxidation of surfaces. The high temperatures produced by the exothermic event decompose local portions of samples forming a differentiated flux of partially melted silicate (si-mt) with entrained metal-sulfide (sul-mt) droplets. The si-mt forms crystals of olivine (01) in Ca-rich pyroxene (Cpx) melt that resorbs a portion of iron sulfide (Po). The immiscible sul-mt droplets of (Fe,Ni,Cu)1-xS contain magnetic subsolidus Ni-pyrrhotite (Ni-Po) with Cr-bearing ferrospinel (Mag). Sub-micron sized flecks of Au are found on the surface of a sul-mt droplet with scanning electron microscope (SEM).IntroductionSulfide ore deposits supply the world's mineral resource in the production of non-ferrous metals. Particularly, Cu-Ni deposits are chemically enriched in metals from high sulfur saturation during magmatic formation that creates the proper geochemical environment for metals enrichment [1, 2]. The sulfur and oxygen fugacity control redox conditions of a differentiated silicate/sulfur magmatic melt with the concentration of iron playing a dominate role in the chemical partitioning of metals in sulfide liquid [3, 4]. The initial magnetic crystallization of (Fe,Ni)i-xS monosulfide solution (mss) from metal-sulfide liquid has an exclusive effect on the fractionation of mineral assemblages (zoning) [5].Phase equilibria of sulfide melt (sul-mt) components are related by a miscibility gap with mss forming Ni-rich pyrrhotite (Ni-Po) followed by the crystallization of (Fe,Cu)1-xS intermediate sulfide solution (iss) [6]. Precious metals form stable chacogenides and are retained in solution until the final liquid solidifies. The redistribution of metals now occurs by subsolidus cooling of mss and iss that exsolve low-temperature Fe-Cu-Ni bearing mineral assemblages [7]. The proper interpretation of ore genesis increases processing capabilities by isolating chemically enriched zones during extraction and should be used to aid in sustainable mine site development [8-11]."

Jan 1, 2013

By H. Y. Sohn

A novel solvent extraction process in which the emulsion is generated by bottom gas injection rather than mechanical stirring has been developed. This process has a number of advantages over the mixer-settler unit or the spray column in terms of simple equipment configuration and the ease of cleaning and process control while providing a large interfacial area for mass transfer. The equipment consists of a horizontal cylindrical vessel in which the two immiscible liquids flow countercurrently. High-strength gas jets are injected from the bottom at certain intervals along the length of the vessel. The gas jet creates a plume zone consisting of an emulsion of the two liquids which contains a large interfacial area for rapid mass transfer. The two liquids then disengage and flow in the opposite directions before entering another plume zone. Thus, the process combines the simplicity of a cylindrical vessel, having no moving parts, with the contacting efficiency of a mixer-settler. The gas can be recycled in a closed loop, thus eliminating mist and other emission problems. These advantages would be especially significant for treating large-volume/low-value liquid streams which contain hazardous substances and/or suspended solid particulates.

Jan 1, 1996

By William Petruk

The concentrator of the Iron Ore Company of Canada consists of spiral circuits, a cone plant and a magnetics plant with regrind. The proportions of liberated and unliberated grains of iron oxides at each point throughout the concentrator were measured by image analysis, and recoveries were calculated for each particle type by the MATBAL materials balancing program. The results show that spirals and cones recover more than 92% of the liberated iron oxide grains in the size range of 848 to 150 um,, but the recovery drops off rapidly for finer grained particles. The tailings from the spirals and cones are reground and low intensity magnetic separators are used to recover liberated magnetite in the -37.5 um size range. The concentrator does not have a unit that efficiently recovers iron oxide grains in the size range of 150 to 37.5 um Consequently about 25% of the iron oxides in the ore are lost to tailings as liberated. grains in the size range of 150 to 37.5 um

Jan 1, 1989

By J. A. Holmes

Due to varying and complex mineralogy, the flotation tailings from the Chingola Concentrator have, for some years, contained upwards of 0.4% acid soluble copper. In 1968, an investigation was initiated, to determine a method for recovering this acid soluble copper. This initial investigation concluded with a recommendation to install a leach-solvent extraction-electrowinning plant at Chingola, to treat up to 900 000 tonnes of material per month, for an additional copper production of some 4 500 tonnes per month. The process consists basically of six stages :- Materials reclamation handling and preparation, acid leaching in air agitated pachucas, solid-liquid separation by countercurrent washing in thickeners, solution concentration and purification by solvent extraction, copper recovery by electrowinning, and residue neutralisation and disposal. This paper describes the development of the main parameters for design of each of the six sections, and gives details of the final plant design. Problems encountered in commissioning and initial operations are commented on, particularly insofar as they indicated any errors or misjudgements in the design. The choice of materials of construction is commented on in some detail.

Jan 1, 1976

By M. Soltanieh

The liquidus surface? and tie-lines in the nickel-cobalt-sulphur ternary system have been determined between 1<273-1573 K. The experiments were conducted by equlibrating the liquid sulphide with the metallic alloy phase. The liquid sulphide phase was sampled and chemically analyzed. The alloy was analyzed by electrol} microprobe. Combining the present results with the.avai1abl~ literature data, the thermodynamic properties of this system were calculated.

Jan 1, 1998

By Mohamed Ahmed, A. Kawy

"Smelting of scrap copper and residual anodes and cathodes carried out in a reverberatory type furnace. In this, deoxidation process is carried out by wood, which acts as a resource of reduction gases such carbon monoxide, hydrogen and methane. Use of wood causes the formation of soot pollutants and efficiency of oxygen removal from copper is low leading to added costs in removing contaminants. This expensive problem was solved by using of reformed natural gas as a source of reduction gases (CO+ H2).IntroductionThree reverberatory furnaces were used for smelting of scrap copper and residual anodes and cathodes. Each furnace had a 7tpd capacity and was operated at 1183 °C.In this furnace, Step1-compressed air supplied by tubes from the side of the furnace to remove sulfur from copper matte by oxidation .The copper is also oxidized to copper oxide .[1]Step 2- copper from matte is deoxidized by a reductant. Typically deoxidation process is carried out using wood as a resource of carbon monoxide, hydrogen and methane which are the reduction gases. Use of wood causes the following:1- Forms soot pollutants2- Oxygen removal efficiency from copper is low; more contamination in copper matte increased energy in deoxidation3-the process is highly expensive.In the recent trends, this problem has been solved by using reformed natural gas as a source of reduction gases (CO+ H) .This results in 1-Reduced pollution during smelting.2- High efficiency in the removal of oxygen from copper to produce oxygen free copper. The surface of copper produced from this method is smooth which helps in forming and machining.3- Low cost and natural gas is more readily available in Egypt than wood."

Jan 1, 2010

By C. Flores

A novel process using solid metals for the direct reduction of more noble metal ions from solvent extraction organics has been developed. Base metals recovery has been the principal focus of investigations to date but feasibility tests have now also been made on galvanically stripping selected precious metals. In this study gold (III) was loaded from an aqueous HAuCI4 .3H20 solution into a mixed organic 40 vol.% TBP, 10 vol. % D2EHPA in kerosene. The direct precipitation of metallic gold from the loaded organic phase using zinc powder and iron, aluminum and copper slabs at 70 °C was successfully demonstrated. The gold reduction rates were relatively fast even though the conductivity of the organic solutions is very low. The reaction rates were studied as a function of the variables zinc particulate size, oxygen and nitrogen atmosphere, water content in the organic phase, organic ratios and temperature. The gold morphology was usually powdery or dendritic in nature but continuous films were obtained in some instances. Activation energies were calculated and possible reaction mechanisms are discussed. In general, the results obtained were very promising and showed that gold can be successfully cemented from selected organic solvents by galvanic stripping using less noble solid metal reductants.

Jan 1, 1995

By Sheng Dai, Yuan Lee, Haiming Xiao, J. P. Young

"There are numerous analytical applications of scatter-emission and/or absorption spectroscopy applied to liquids and solids in the temperature range of 0 to 350°C. In this paper an all-silica fiberoptic probe is described which is useful for spectral analyses from 0 to 1600 K and can be used in harsh chemical environments. The probe has been used for Raman spectral analyses of many molten salt and solid material systems to 1000°C. It has applications for such studies at higher temperature ranges. The instrumentation required along with the demonstrated and proposed applications of the all-silica probe are presented and discussed.IntroductionThere are many kinds of scatter-emission spectroscopies that are of value for analytical measurements. Fluorescence, reflectance, arc or spark emission are descriptors for some of these. Raman scatter spectroscopy is also quite a useful technique for analytical measurements.In Figure 1, we give a simplified explanation of the Raman effect. If one shines monochromatic light into a sample, light may be absorbed, exciting the sample to some virtual state. We know from experience that almost all of the light is re-emitted in the same wavelength range. This is called Rayleigh or Mei scattering and is designated in the figure by the arrows in both examples that point up and down from the same lower energy state. A very small percentage (the order of 10-4%) of the monochromatic light is re-emitted leaving the sample at a vibrationally-excited state. Thus, this light is at a distinctly lower energy compared to the exciting radiation. This is called a Stokes shift and is represented in the left-hand example by an arrow descending to a more energetic vibrational state. If the sample is not at a temperature of absolute zero, some of this vibrationally excited state will be thermally populated. That portion of the sample still absorbs and re-emits exciting radiation as Rayleigh scattered light, but a small percentage of the exciting light is re-emitted as the sample relaxes to the lower vibrational state. The energy of this light is of higher energy and is called an anti-Stokes shift, depicted in the example to the right. Notice that the energy separation of the Stokes or anti-Stokes shifted emission from that of the exciting radiation is the same, and expressed in ~cm-I. The intensity of either shifted emission is a function of the population of the vibrational energy states; therefore, the ratio of the intensity of Stokes to anti-Stokes signal varies with absolute temperature. We will come back to this point later."

Jan 1, 1997

By Donald Voit

"The reaction between zirconia/zircon, coke, and chlorine involves a slow reaction between the coke and the zirconia/zircon and a fast reaction with chlorine. Because of the fast chlorine reaction, the reaction rate for zirconia/zircon is nearly independent of chlorine concentration for most conditions. The reaction between zirconia/zircon and coke is particle size controlled and related to the degree of physical contact between the zirconia/zircon and the coke. Since particle-particle contact is critical, compaction of finely ground coke and zirconia/zircon produces the highest reaction rates. Uncompacted, coarse coke and zirconia/zircon has the slowest reaction behavior with static bed tests.SummaryZirconia reacts with chlorine in the presence of carbon to form zirconium tetrachloride, carbon monoxide, and carbon dioxide. A similar reaction occurs with zirconium silicate with the additional formation of silicon tetrachloride. The reaction rate depends primarily on temperature and the intimacy of contact between the zirconia and the coke. The reaction is multi-stepped with a slow reaction between coke and zirconia to form an intermediate that reacts rapidly with chlorine, causing the order of the reaction for chlorine to be near zero. Chlorination rates in the range of 1 µmole/hr/cm2 are seen for fluid bed reactors. Plug flow, and static bed reactors have reaction rates of the order of 1 mmole/hr/cm2, where the area is based on the zircon surface area in plug flow and fluid bed reactors and the boat cross sectional area in a static bed. Chlorination rates measured in zirconia/coke briquettes are higher with rates as high as 400 mmole/hr/cm2 reported. High chlorine diffusion resistance, not accounted for in the analysis of experimental results, has led to a lot of confusion in the literature interpretation of chlorination data.In general coke and zirconia/zircon particle size, coke and zirconia/zircon intimacy, coke to zirconia/zircon ratio, chlorine concentration, and temperature are important variables for chlorination. Decreasing the coke and zirconia/zircon particle size generally increase the reaction rate. The coke to zirconia/zircon ratio affects the reaction in a more complex way. Increasing the chlorine concentration generally increases the reaction rate, but the effect appears to be more related to the concentration dependency of diffusion than to its role in the kinetics. The reaction rate increases with temperature but the exact behavior is complicated by temperature effects on diffusion."

Jan 1, 2011