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By D. G. C. Robertson

The thermodynamics and kinetics of the reactions involved in fuming zinc from oxide slags using coal or coke were first studied in 1955 and have been the subject of many investigations since that time. The key reaction is ZnO(in slag) + CO Zn(g) + COl. This paper will review the some of the recent work, and will add new insights obtained in experiments carried out by the authors. In the first series of experiments it was shown that the reaction 2Fe2+ + ZnO = 2Fe3+ + Zn(g) or 2FeO + ZnO = Fe2O3 + Zn(g) does not occur at an appreciable rate, as is expected from thermodynamic considerations. In the second series of experiments it was shown that zinc does not fume from the slag at a significant rate unless a reductant has been added. This again is in accord with thermodynamic considerations, but is in contradiction to some of the experimental results reported in the literature. A third series of experiments was carried out with excess coke being present, so that the rate of supply of reductant was not in any way controlling the rate. The kinetics of zinc oxide reaction were then found to be independent of the zinc oxide concentration, but increased with increasing basicity, and temperature. The presence of high concentrations of FeO in the slag also improves the kinetics. At low zinc oxide concentrations iron oxide reduction occurred in parallel with zinc oxide reduction. We propose that (under the conditions of this work) the kinetics were controlled by a chemical step, namely the rate of desorption of an adsorbed CO2 species. This is the same mechanism as reported by Belton and co-workers for the kinetics of the reduction of FeO. This explains why the reduction of metal oxides in slags by hydrogen is often faster than by CO.

Jan 1, 2003

By Robert D. Rogers

The demand for phosphate will continue into the future, because phosphate is currently irreplaceable as a plant nutrient and in many chemical applications. Phosphate is not recycled, so the supply must be replenished through a process of mining and purification. Numerous microbial isolates. obtained from the environment were screened find those which demonstrated the greatest promise of solubilizing PO4 from the ore of interest. Screening was accomplished in a step wise manner an agar plate bioassay, shake flask studies, and semi continuous growth conditions. It was found that with the proper conditions of nutrient supply and solution pH; the bacteria and. fungus used in the semicontinuous process were able to solubilize in excess of 80% of an Idaho rock phosphate ore (RP) within nine days. A significant amount of solubilization occurred within the first six days. There was a 'reasonable correlation between the occurrence of soluble Ca and PO.4 during the processing of the RP thus providing evidence that the RP was being disintegrated by the organisms. In all cases, HPLC analysis of the solutions in which PO4 had been. extracted from RP showed that organic acids, which have been implicated as the mechanism of solubilization, were present.

Jan 1, 1991

By Edgar Peek

Lixiviant regeneration is by definition a precondition for any hydrometallurgical process. In chloride hydrometallurgy either HCl or Cl2 has to be regenerated in order to establish an economically viable metallurgical process. One such regeneration process is widely used with steel pickling where HC1 is regenerated through the thermal decomposition of ferrous chloride in either spray roasters or fluid bed pyrohydrolyzers. This standard HC1 regeneration process deserves to be considered as a potential separation process, since thermodynamic calculations show that a fluid bed pyrohydrolyzer can function as a ferrous-nonferrous separator. Several nonferrous,metals such as zinc, lead and cadmium can be volatilized as a chloride under ferrous chloride pyrohydrolysis conditions. If such a nonferrous metal volatilization could be achieved in the case of slurry feeding of "contaminated" iron oxides, then this would increase the Fe/H2O ratio of the (process) feed and thus save on fuel per ton of iron, while yielding a marketable iron oxide product. Previous test work on synthetic materials revealed that the near-complete separation of zinc, lead and cadmium from iron oxide was possible in a pyrohydrolytic atmosphere, even if zinc was present as zinc ferrite (more than 99.5%). This investigation, which was carried out in a tube furnace at 1100 K has now been extended to treat synthetic zinc minerals and also franklinite ore. For the latter, it was found that 85% zinc volatilization could be achieved in 4 hours at 1300 K. It is postulated that complete zinc volatilization could not be attained due to the formation and/or presence of gahnite and hardystonite, which might be stable in HCl/H2O atmospheres at 1100 K. The effect of adding small amounts of calcium chloride to react with gahnite and hardystonite to give zinc chloride and both calcium aluminates and silicates is being discussed. Test work on slurry feeding of this complex ore in a recently constructed 4-inch diameter fluid bed pilot unit has been planned for the near future.

Jan 1, 1995

By Hong Yong Sohn

A thermodynamic and experimental investigation has been performed to develop a new process for converting sulfur dioxide to elemental sulfur by a cyclic process. The most promising new process is a cyclic reaction scheme involving calcium sulfide and calcium sulfate. In this process, the reaction between sulfur dioxide and calcium sulfide produces elemental sulfur vapor and solid calcium sulfate. The latter is reduced by a suitable reductant such as hydrogen to regenerate calcium sulfide. 'Experimental results showed that up to 60 % of calcium sulfide powder was converted to calcium sulfate in 10 min at 1153 K under a sulfur dioxide partial pressure of 25.8 kPa. More than 95 % of nickel-catalyzed calcium sulfate powder was converted to calcium sulfide in 20 min at 1123 K under a hydrogen partial pressure of 86.1 kPa, water vapor being the only gaseous product. Sulfur dioxide-containing streams from certain new sulfide smelting plants contain much higher partial pressures of SO2. The rate of the first reaction is expected to be accordingly higher than in the test conditions reported in this paper.

Jan 1, 2002

By Arpad E. Torma

The identification and characterization of lithographic iron and sulfur oxidizing bacteria in the 1940' s. opened up new possibilities and challenges for the mining and metallurgical industries. These were exploited during the 1950's and' 1960's, when it was demonstrated' that mining wastes and complex unused mineral resources could be economically treated by bacterially assisted heap and dump leaching processes?. During the 1970's this technology grew into a more structured discipline called "biohydrometallurgy". In the l980's efforts were devoted to the identification of a variety of organisms involved in naturally occurring leaching processes. Further efforts dealt with the elucidation, of leaching mechanisms; the leach ability of nickel, coban, zinc, and precious metals; the desulfurization of coal; and diverse biosorpion phenomena. The application of genetic engineering techniques for the improvement of microbial performance was also initiated?. Current trends in biohydrometallurgy include improvement of many of the techniques noted above, as well as application of leaching. technolog.ies to. environmental remediation scenarios. These activities afford considerable opportunities for research in the 1990's. For example, bioremectiation of abandoned mining and processing sites requires development of new and economically viable technologies capable of removing low concentrations of toxic metals from high volumes of solid and/or liquid wastes.

Jan 1, 1991

By Luciano B. Oliveira, Angela O. Costa, Sergio N. Monteiro, Luis Guilherme C. Marques

"Biofuels are gaining a relevant role in today’s world not only as a solution for the decreasing petroleum reserves but mainly as a positive contribution to the efforts in global warming mitigation. In Brazil, since 1975, the replacement of gasoline by ethanol started a so-called PROALCHOOOL program, which is now being complemented with the replacement of petroleum diesel by biodiesel. This biodiesel program was officially created in 2005 with mandatory goals, supported by legislation, of 2% addition in 2008 and 5% addition in 2013 into all commercialized regular diesel. In this work, a critical analysis of the Brazilian biodiesel program is presented. The technical aspects related to the different raw materials, including wastes, available for biodiesel conversion as well as the economical conditions associated with production costs and market logistic are discussed. The environmental benefits associated with the retention of greenhouse gases are also discussed.IntroductionToday the commonly accepted fact that the petroleum world reserves are probably passing through a maximum and start declining in terms of the total amount that can be extracted by existing technologies is motivating significant changes in our society. The continuous increase in the price of gasoline and other liquid fuels is an immediate worrisome and visible consequence. However, more than an economical problem, our civilization is already facing the effects of global warming, due to CO2 emission from burning fossil fuels, mainly from coal and petroleum. It is now realized that a large scale solution for these problems demands the prompt substitution of non-renewable fossil fuels by others that, in addition of being renewable, have a relatively lower contribution to the greenhouse gases."

Jan 1, 2008

By Senlin Xie, Wanlin Wang, Lejun Zhou

"The innovative development of multiphase slag in hot-metal treatment has attracted considerable attention due to the reduction of CaO consumption and minimal environmental emission. In order to improve the efficiency of dephosphorization and to reutilize the waste-slag as an alternative source of phosphate ores, it is important to increase the distribution ratio of P2Os between the solid solution (2CaO· SiO2-3CaO· P2O 5) and liquid slag. An investigation was carried out to study the effects ofNa2O and B2O3 on the distribution ratio of P2Os, the results indicated that the increase ofNa2O would enhance the distribution ratio of P2Os with the formation of solid solution (2CaO·SiO2-Na2O·2CaO·P2Os), while B2O3 has the opposite function, and changes the morphology of solid solution. The study would provide an instructive way for the design of multiphase slag and re-utilization of waste-slag.IntroductionIn order to meet the increasing demand for high quality low-phosphorus steel, it requires a high efficient hot metal dephosphorization process. The current slag system for hot metal treatment contains large amount of solid CaO dispersed in liquid slag, which introduced a large amount of CaO consumption due to its low solubility, especially when CaF2 was restricted due to the environmental concerns. Therefore, new refming method to improve the utilization efficiency of CaO by using a solid/liquid coexisting multiphase slag was proposed, and the studies regarding to solid solution formation mechanism, mass transfer behavior of phosphorus and the phase relationship for multi-phase slag have been conducted. [1-6]Normally, hot metal dephosphorization slag consists of CaO--SiOz-FeO--P2O 5, and it has been approved that 2CaO·SiO2 forms a solid solution with 3CaO·P2Os at the hot metal treatment temperature over a wide range of compositions. [7] Kitamura et al [8] pointed out that the (2CaO·SiO2-3CaO·P2O 5) solid solution plays an important role in dephosphorization, and it has been regarded as an absorbents for phosphorus to lower the phosphorus content in liquid phase, which makes it more capable for future dephosphorization. l Besides, the multiphase slag has the potential to be recycled as a source of phosphorus, if the (2CaO· SiO2-3CaO· P2O 5) solid solution could contain high phosphorus content, and it can be separated from FeiO matrix 8hase due to the large difference of their magnetic properties under the strong magnetic field. [10, 11]"

Jan 1, 2014

By Osamu Iida

Since 'start-up of the larger Mitsubishi Continuous Copper Smelting Process in 1991, furnace relining campaign was gradually prolonged to once every 2 years according to deregulation of governmental boiler inspection. On the other hand, in 1998 Naoshima smelter embarked on an intermediate strategic expansion plan to strengthell its international competitiveness. As part of this plan, modifications were implemented in the copper smelter designed to increase output of anodes from new charge source to 270,000 tpa. In May 1998, treatment of dried neutralized residue was started in C furnace, and during the shutdown for brick relining in April 1999, intensive modifications to the boilers as well as the installation of new spray coolers for furnace off gas treatment were implemented. Finally, the new larger oxygen plant was commenced its operation in May 2000 and the expansion was achieved around 30% increase of anode production from original design.

Jan 1, 2001

By D. Lui, B. G. Thomas, B. Ho

"Results from mathematical models and plant experiments are combined to quantify the effect of transverse depressions and oscillation marks on heat transfer in the continuous casting mold. A heat transfer model has been developed to calculate transient heat conduction within the solidifying steel, coupled with the steady-state heat conduction with the continuous casting mold wall. The model features a detailed treatment of the interfacial gap between the shell and mold, including mass and momentum balances on the solid and liquid powder layers. The model predicts the solidified shell thickness down the mold, temperature in the mold and shell, thickness of the resolidified and liquid powder layers, heat flux distribution down the mold, mold water temperature rise, ideal taper of the mold walls, and other related phenomena. The important effect of non-uniform distribution of superheat is incorporated using the results from previous 3-D turbulent fluid flow calculations within the liquid cavity. Results from plant experiments confirm that transverse surface depressions and oscillation marks form at the meniscus and move down the mold. Measurements of mold thermocouple temperatures and breakout shell thickness were used to calibrate the models. The results indicate that the surface depressions and oscillation marks are filled with mold flux, but still have a significant effect on decreasing heat transfer. The predicted mold temperature fluctuations are consistent with measurements. If the depressions become filled with air, their effect is greatly increased. These results should be useful in the difficult task of interpreting transient mold thermocouple signals for on-line quality monitoring.IntroductionMany different types of intermittent surface defects on steel slabs arise during initial solidification in the mold of the. continuous casting machine. These defects include deep oscillation marks, surface depressions, and cracks. They may lead to quality problems, such as slivers, in the final rolled product. In severe cases, breakouts may occur, where liquid steel bursts through a thin section of the shell and drains over the casting machine below the mold."

Jan 1, 1997

By S. P. Rivers

The stainless steel industry re1ies on nitric-hydrofluoric acid (HNO,/HF) pickling solutions to remove surface contaminants and maintain the corrosion resistance of the steel. More stringent environmental guide1ines are expected to be placed on the disposal of these solutions which could significantly increase processing costs. The U.S. Bureau of Mines has been conducting research to develop a process for recycling depleted pickling solutions, thus reducing the quantity of by product acids generated. Research has shown that F- can be liberated from the predominant iron fluoride species (FeF,') by using oxalic acid in an electrodialysis cell. Ion selective membranes allow dissolved metals in the depleted solution to be replaced with hydronium ions by metathesis, thereby regenerating the HF. The regenerated HN03/HF is then retained in the pick1ing solution. This paper reports on the research effort at the U.S. Bureau of Mines Rolla Research Center to apply electrodialytic recycling to HN03/HF pickling solutions.

Jan 1, 1993

By Stefan Mutl

By the term sorting one understands the separation of a material mixture into two or several products according to different material characteristics in the preparation technology. The oldest sorting procedure, the handpicking, is less and less used to separate different material mixtures because of the considerable personnel expenditure and the strict hygienic regulations at the workplaces in Europe. In general, the manual assortment is able to solve separation tasks, which could not be solved by machines so far. The picking is one of the most selective processing methods. However, the progress in the computer and sensor engineering today makes the creation of automatic picking devices possible, whose efficiency goes far beyond the possibilities of handpicking. Therefore in the future automatic picking will not only be applied to already common applications like the waste glass assortment by colour, but also to the assortment of complex composed material mixtures e.g. old shreddered cars. Thus, the automatic picking, supported by high performance computer systems and new sensor technology, gains more and more significance within many applications of waste processing. However, in order to apply automatic sorting procedures for different material streams within recycling processes, a substantial research and development need still is existing. The desire of the users is to sort more extensively in order to achieve products with bigger material varieties, In addition, the requirement of the accuracy of recognizing and sorting out of single grains rises, This lecture illustrates the procedure of the hand picking before it was employed in waste processing. Thus, a renaissance of a long forgotten method is happening in terms of today's state of the art procedure "automatic picking". Possible technologies, fields of application and future potentials of this technology are pointed out.

Jan 1, 2003

By Sung-Mo Jung

Experiments were carried out on a system with artificially prepared slags in a graphite crucible, in order to examine the possibility of recycling BOF slags produced in the steelmaking process. More than 80% of FeO and P2O5 was reduced within 20 minutes and the FeO reduction rate was greater than that of P2O5. P2O5 reduction began after more than 60% of FeO was reduced. Increasing slag basicity enhanced the reduction of FeO and P2O5. Temperature also improved slag reduction. The overall reduction rate was controlled by the chemical reaction at the slag/carbon interface. The reduction rates of FeO and P2O5 were second and first order with respect to their respective contents. Most of the reduced phosphorous is believed to vaporize in the form of P2 gas.

Jan 1, 2006

By Alexey T. Kovalev, Irina A. Khabarova, Valentine A. Chanturiya, Igor Zh. Bunin, Elizaveta V. Koporulina

"The paper presents new theoretical and experimental results about mechanisms of disintegration of mineral complexes and structural transformations of the sulfide surface under high-power nanosecond electromagnetic pulses (HPEMP). The heated gas outflow from nanosecond breakdown channels of sulfide minerals under HPEMP is considered. It is shown that the gas outflow from channels can be an additional destructive factor in the processes of the electric pulse discharge disintegration of mineral complexes. It is shown that the effect of HPEMP changes chemical surface composition and, respectively, technological properties of pyrrhotite and pentlandite. Morphology and elementary composition of new micro- and nanoformations on mineral surface of pentlandite and pyrrhotite have been investigated using up-to-date methods of SEM/EDX and Scanning Probe Microscopy. Preliminary electropulse effect on mineral products before flotation allows producing optimal conditions for flotation separation of pentlandite and pyrrhotite owing to forming the new nanophases and defects on the surface of sulfides.IntroductionThe effectiveness of High-Power Nanosecond Pulses in the disintegration and liberation of fine disseminated mineral complexes and the recovery of micro- and nanoparticles of precious metals from refractory ores was demonstrated in [1, 2]. Possible mechanisms of selective disintegration were considered in [1-3]. It has been shown both theoretically and experimentally that electric breakdowns can play an important role in the nanosecond pulsed treatment of milled minerals (e.g., semiconductor sulfides and quartz with particle sizes of 100 µm to 2-3 mm) that are carriers of finely disseminated gold and other valuable components. Electric discharges in such minerals are accompanied by a destruction of integrity in the form of breakdown channels and the formation of a system of cracks around these channels [3]. The development of the domains of induced cracks around the channels is determined by the pressure of evaporated material in the breakdown channel. Upon an instantaneous energy release in a channel (nanosecond discharges), the change in its transverse size and in the gas density and pressure in the channel is determined by (i) the radial motion of the evaporation wave, (ii) the radial expansion of the channel, and (iii) the heated gas outflow from the channel. The evaporation wave moves with a speed on the same order of magnitude as the speed of sound (or greater) and travels a distance of around the initial channel radius, i.e., a much smaller distance than the breakdown channel length."

Jan 1, 2011

By Lawrence L. Brown

As part of the Federal effort to help maintain an adequate supply of fertilizer materials, the Bureau of Mines conducted research to characterize complex low-grade Michigan phosphate materials and to devise methods for recovering fertilizer-grade phosphate concentrates. The rock is from middle Precambrian sedimentary formations in the Marquette Range located in the central part of the Upper Peninsula of Michigan. Occurrence of phosphate-bearing sediments in Precambrian rocks is rare. This deposit, containing 12 to 15 pct P2O5 is believed to be the richest Precambrian phosphate deposit in the United States. Petrographic examination showed that the conglomeritic rock contains crystalline apatite both in "black pebbles" and in quartz matrix. Attrition scrubbing and sizing tests showed that there is no tendency for phosphate to concentrate in any of the sized fractions. In beneficiation tests, which included grinding to minus 325 mesh followed by phosphate mineral flotation using a fatty acid-fuel oil collector, a phosphate concentrate was obtained that had a grade of 30 pet P2O5 and a P2O5 recovery of 72 pct. This concentrate should be suitable for fertilizer manufacture.

Jan 1, 1982

By Xiping Chen, Wangxing Li

"Spent potlining is unavoidable solid waste from aluminum smelters. About thirty kilograms spent potlining is discharged in China to produce per ton primary aluminum. Spent potlining has high level soluble fluorides and cyanides so that it brings heavy pollution to environment. It is prohibited to keep a large amount of spent potlining in open air because it will lead concentrated pollution to local soil and water source due to hydrated reactions between spent potlining and rain water/moisture in air. Landfill may solve pollution of spent potlining provisionally, but it is difficult to be accepted by aluminum smelters because of its high investment, troublesome monitoring and perennial maintenance. Detoxifying of spent potlining not only can remove deleterious fluorides and cyanides in SPL, but also can make fluorides in SPL recycle and return to aluminum electrolysis cells, at the same time benign SPL solid residue can be recycled and ready for cement production.IntroductionChina became the largest primary aluminum manufacturer in 2001. In the past few years, its aluminum output increased by twentyfive percent every year and reached 12.56 million metric tons in 2007. The whole world was very surprised and focused attention upon Chinese aluminum industry. It is more and more important to keep sustainable and steady development with the rapid development of Chinese economy. Aluminum industry is an important base industry and does a great contribution to Chinese economy. But aluminum industry is high energy-consumption and heavy-pollution industry. The government has paid more attention to aluminum industry in recent years. Nowadays the bothersome problem which counterworks Chinese aluminum industry is pollution from solid wastes. Main Solid wastes from aluminum industry are red mud from alumina refineries and spent potlining (short as SPL) from aluminum smelters. Spent potlining are waste lining materials from aluminum electrolysis cells. During production of aluminum, due to reactions between melted electrolyzer and pot lining as well as penetrating of fluorides into pot lining, newly-formed compounds inlayed in pot lining, destroyed the lining structure and brought pot lining cracking. Melt rushed out of lining cracks, cells have to be stopped running and ready for heavy repair. Cell life generally varies from 1500 to 2000 days. Spent potling is an unavoidable solid waste from aluminum industry."

Jan 1, 2008

In accordance with the new concept described in the paper presented at the TMS annual meeting in 1989, 1 a new zinc cellhouse was constructed and successfully operated. The new concept was proposed in order to reduce energy requirements and to mechanize the electrode handling in the cellhouse. Major modifications involved the use of an electrode unit consistfog of assembled anodes and cathodes with frame bodies between each cathode and anode. The space between a cathode and an anode could be halved by this unit structure. In this paper actual operation data are summarized and discussed in comparison with the calculated figures.

Jan 1, 1990

By N. V. Gorelikova

A new type of zirconium mineralization has been recognized in the Devonian volcanic rocks from an orogenic depression in the Central Kazakhstan. The most characteristic features of this deposit are the fine-grained nature of the zirconium mineralization, an unusual texture of the zirconium ores, and a close association of zirconium with phosphorus in the ores. Zircon grains form fine globular aggregates with the features of hexagonal crystal habit. In addition to crystalline zircon, the ores contain metacolloidal zircon, similar to hydrozircon. The morphological and textural features of the zirconium ores suggest that the deposition of ore deposits took place at a low temperature from colloidal solutions. It is believed that this deposit should be considered to be a new type of zirconium mineralization that is related to low-temperature hydrothermal processes.

Jan 1, 1995

By Marco Olper

After two years of extensive research a new and innovative modification to the CX-EW process has been exploited. This process, called CX-EWS, avoids completely all the critical aspects of the previous process which affected the cost of the energy, of the chemicals and of The maintenance of the insoluble anodes. All these benefits reflect a saving of about 30% of The operating costs compared to the present traditional production and allow for a total operating costs of less than 6.5 cts/lb. lead (net of raw material cost). With this new technology it is allowed for the first time the treatment in the same plant facilities of both primary lead sulphide concentrate and spent batteries. The paper describes the technical and economical aspect of the new process with a feasibility study for 150,000 t/y spent battery facility throughput.

Jan 1, 1995

By Simon N. Lekakh, D. G. C. Robertson

A new integrated CFD-combined reactors approach is proposed for the description of processes in metallurgical vessels. CFD simulations were used to obtain the melt flow pattern in the vessels (ladle, tundish, and continuous caster mold). From these simulations, the characteristic curves were derived: (i) the residence time distribution curves (RTD) for flow-through systems (at tundish exit or at dendrite coherency surface in the mold) and (ii) the mixing curves for closed systems (ladle). In the next step, the melt flow was represented in a “combined reactors” system consisting of a combination of unit reactors (Plug Flow, Mixer, and Recirculated Volume). An inverse simulation was used to define the volumes of the reactor units and the melt flow rates between them by fitting to the characteristic curves from both methods (CFD and combined reactors). The suggested approach is demonstrated for multiple designs of Ar-stirred ladles, tundish, and SEN. This methodology can be used to enhance traditional post-processing CFD analysis and also as a tool for on-line process control.

Jan 1, 2014

By M. Potesser

In the primary and secondary copper industry the anode furnace is the most important process step in the refining procedure to reach an enhancement in value and quality of the copper by a selective oxidation and reduction. By combining the advantages of the conventional tilting hearth anode furnace and the benefits of the drum type anode furnace a new aggregate was developed and patented. The cross-section of the furnace is elliptical and the whole unit is tiltable. During the melting period, the contact surface between the burners and the bath or the scarp is enlarged - an increased energy input is the consequence. For the refining period the furnace is rotated, whereby a high bath level is guaranteed. Due to the longer residence time of the gas in the copper melt, not only the gas consumption is reduced but also the efficiency/quality of the refining process is improved. This investigation shows a metallurgical comparison between the new anode furnace concept with the elliptical profile/cross section and the conventional, tiltable hearth anode furnace as well as the drum type anode furnace. The CFD modeling of the currents in these different furnaces delivered helpful data to compare the geometry of the different furnaces. The investigation covered the refining of blister copper from primary metallurgy, from secondary metallurgy as well as from a mixture of both copper melts. The paper underlines the possibilities for a reduction of the tap-to-tap time and for an increase in production capacity, which can be achieved by applying the new furnace concept in comparison to the conventional furnaces.

Jan 1, 2006