Search Documents

By A. D. Zunkel

Increasing amounts of electric arc furnace dust (EAFD) are being generated worldwide as more steel is produced from electric furnace melting of galvanized steel scrap. In most countries, the management of this material is a costly technical, economic, and legal problem for minimill steelmakers. Many technologies and processes are being developed and implemented worldwide to manage this material to recover contained zinc, lead, and iron values and render it nonhazardous. These processes are pyrometallurgical, hydrometallurgical, or hybrid in nature. Some produce zinc oxide, some zinc metal, some lead metal, and some lead cement. Some are successful, some have failed, many are dormant. or abandoned, and others continue to be developed and emerge. This paper updates the current status of 20-30 processes in various stages of commercial application and development used worldwide to manage EAFD and recover its nonferrous, particularly zinc and lead, and ferrous values.

Jan 1, 2000

By X. Jay Gao

A fast high-temperature carburizing process integrated with materials design and optimization via a systems design approach was developed to significantly reduce process cycle time. Process experiments were focused on boost cycles to obtain a robust boost process and investigate surface reaction kinetics, primary carbide formation and dissolution. Weight gain and microhardness were measured, all showing evidence of non-monotonic time evolution for longer boost times at higher temperatures. Optical and electron microscopy and other techniques have been used to identify possible carbides, their location and types. These results assist the picking of first boost time with least variation rate in terms of content of case carbon and carbides, dissolvable in subsequent diffuse if any. The results also provide critical information to properly formulate surface reaction kinetics and diffusion and formation kinetics of carbides modeled using DICTRA. Keywords: high temperature vacuum carburizing, partial pressure carburizing, heat treatment, process development, carbide, case hardening, microstructural analysis, over carburizing

Jan 1, 2003

By D. V. Hughes, J. R. Nyberg

"Since 1985, a comprehensive automation system has been installed at the Outokumpu Oy Zinc Plant, Kokkola, Finland. In leaching and solution purification special sample handling equipment, on-line analyzers and instruments, and a computer-based control system with duplicated supervisory stations have been installed. The system has enabled closer control of the process and more efficient use of labor. Since its installation recovery of zinc has improved, and use of zinc dust, steam, and water have decreased. The system has performed reliably. It includes optimizing programs and process study tools, which facilitate improving process performance. An expert system has been built-up to prompt process personnel to take appropriate action on the basis of process data. In electrolysis a similar system, based on extensive monitoring of the process and of production of zinc cathodes, is used to maximize- current efficiency by maintaining optimum conditions in the process. It is planned that in the future the control systems will be integrated and extended to cover the roasting plant and effluent control.IntroductionThe Zinc PlantThe Zinc Plant of Outokumpu Oy Metallurgical Division at Kokkola, on the West Coast of Finland, has grown from a 90,000 t/a plant founded in 1969 to become, with its present capacity of 170,000 t/a, one of the world's ten largest zinc plants. Especially since the completion in 1988 of a thorough modernization programme, it is also among the world's most modern.The Kokkola plant takes its raw materials from Outokumpu's own mines, Vihanti and Pyhasalmi in Finland, and Tara in Ireland, and from outside sources. Concentrates are roasted in two Lurgi fluid-bed furnaces, and the calcine is leached and iron removed by the Conversion process. Following this copper, cobalt, and cadmium are removed, and zinc is refined by electrowinning. The leaching and purification, and the cell-house are automated under computer-based control, and anode and cathode handling in the cell-house are mechanized and fully automatic."

Jan 1, 1989

By Harry Littleton, Jr. Scarber, Wanliang Sun

"The Lost Foam Casting (LFC) process is relatively immature when compared to other casting processes. To make the process more robust, computer modeling is needed to reduce lead times and casting defects. In this study, metal filling of lost foam aluminum castings was visualized using state-of-art real time X-Ray technology. Metal filling of the lost foam casting was simulated using a commercial software package. The result of the computer simulation was compared with the results of the real time X-Ray visualization. Some of the computer simulation results agreed with the real time X-Ray visualization, but some did not. Based on other studies using real time X-Ray technology, new input variables, such as foam density variations, were developed for the computer modeling. With the new variables, modeling of the lost foam casting process becomes more realistic. IntroductionMold filling of the Lost Foam Casting (LFC) process is an important step toward making a quality part. In the LFC process, molten metal is poured against a refractory coated foam pattern surrounded by dry sand. At the pouring temperature of aluminum, the foam pattern is decomposed into 30% (wt) gaseous and 70% (wt) liquid foam pyrolysis products. Existence of the gaseous foam decomposition products significantly increases the back pressure on the metal stream compared with the conventional open cavity sand mold. Entrapment of the liquid pyrolysis products during the metal filling generates many casting defects, such as internal pores, fold and blisters. Existence of these casting defects sometimes seriously degrades the quality of the components manufactured by the LFC process. Understanding and controlling the metal filling of the LFC process will certainly make this process more robust."

Jan 1, 2004

By Guanghui Li

In the paper, the recovery technology of gallium from zinc-leaching residue by cold-bonded coal-based direct reduction process following magnetic separation was developed. The results show that the scattered metal Ga can be concentrated obviously after the reduction of zinc-leaching residue briquette and magnetic separation of reduced product. At the same time, the volatilization of Zn in the residue is enhanced during the reduction. When the residue, bear¬ing 18.60% Zu.21.18% Fe and 527 g/t Ga, was reduced with coal at 1100°C for 150 min, the results of Zn volatilization of 9842% and Ga recovery of 89. 10% were obtained in reduction. After magnetic separation of the reduced product, the concentration of Ga in sponge iron is 2164 g/t, and the separation recovery of Ga reaches 92.42%. The enriched mechanism of Ga during reduction -separation process was studied by using electron microscope, scanning elec¬tron microscope, energy spectrum and mineralogical analysis. The investigations show that there is no formation of independent phase of Ga during reduction process. The Ga occurs mainly in metallic iron phase (the concentration of Ga in metallic iron phase is 0.04%-0,4%), in addition, there exists a little Ga in poorly crystalline sulphide (o.08%-0./5Y& Ow). But Go does not exist in most of glass and silicate phase. The affinity of Ga for metallic iron is the enrichment basis of Go in reduction, and it is also in favor of recovering Go during magnetic separation. Key Words: Gallium Zinc-leaching Residue Cold- Bonded Direct Reduction

Jan 1, 2003

By Nobuyuki Masuda

In Japan, the municipal solid waste, which amounts to 50 million tons, is generated every year and most of it is incinerated. The fly ash from the municipal waste incineration (the primary fly ash) contains heavy metals, such as lead and zinc, etc., and dioxins. In case of melting, the fly ash from the process (the secondary fly ash) contains high concentration of heavy metals (e.g., Zn; 1-20%, Pb, 1-10%). Metal Mining Agency of Japan launched a four-year project in 1999 to establish the integrated technologies to recover the valuable metals from, and to decontaminate, the primary and secondary fly-ashes in the practical scale by utilizing the existing metallurgical processes and facilities, along with the energy saving. The segregation, flotation and chemical treatment are applied to the treatment of the primary fly ash. The secondary fly ash is treated with MY (Mitsui-type blast furnace) Process after the chlorine removal to recover the heavy metals in the ash, In this paper, the segregation and flotation process for primary fly ash and MF process for secondary fly ash are explained. The main results of experiments done from 1999 to the mid of 2001 to design the pilot plants and to optimize the operating conditions are described. The main results of the experiments are as follows: - The segregation reaction of Cu was confirmed by the experiment on the treatment condition of 800 and 900`C with adding oil cokes and water to the primary fly ash, and 99.98% (toxicity equivalent) of the dioxins were decomposed by the treatment. - Washing tests of secondary fly ash to feed MF resulted that more than 70% of chloride were removed, but still lower than expected, and agglomeration tests were successful by the results of the sufficient strength of briquettes produced though a little more binder for the agglomeration is required than usual operation. - Smelting experiment by downsized MF showed that valuable metals, such as zinc and lead, are recoverable in the furnace dust. Recovery ratios, Zn: 58% and 67%, Pb: 74% and 83%, are accomplished.

Jan 1, 2002

By Xinli Wang, Matthew Andriese, Jiann-Yang Hwang, Zhiwei Peng, Byoung-Gon Kim

"The microwave reflection loss (RL) of ferric oxide is studied in the temperature range from 297 to approximately 1400 Kat frequencies of 915 and 2450 MHz. It is shown that the maximum microwave absorption with RL of -38.46 and -35.97 dB can be obtained for ferric oxide having thicknesses of 0.03 and 0.01 m at 915 and 2450 MHz, respectively. The maximum absorption peak with RL below -10 dB is in a 250 K temperature range from 723 to 973 Kat 915 MHz, which shifts to the range between 823 and 1073 K at 2450 MHz. This migration is in good agreement with the variation of the dielectric loss tangent of ferric oxide.IntroductionMicrowave irradiation has distinguishing characteristics such as volumetric and selective heating compared with conventional methods, leading to extremely broad applications in materials heating and processing [1-5].The efficiency of microwave heating was found to be dependent on various factors, such as microwave power [6], frequency [7,8], radiation time [8], applicator geometry [8], sample microwave absorption properties and position as well as dimension [9-11 ], etc. Among these parameters, sample dimension plays an important role but is usually neglected by researchers in microwave processing of materials. In fact, although numerous studies have been directed toward the utilization of microwave energy to assist materials heating and processing, few reports were released on the effect of sample dimension [12,13].This is because all aforementioned factors influencing microwave heating generally exert interactive effects to each other during the heating process, making clarification of the effect of sample dimension difficult. Therefore, it is necessary to propose a parameter or concept for quantifying the effect of absorber dimension on microwave heating, increasing heating efficiency."

Jan 1, 2013

By Junbiao Liu

Rutile is mostly produced from placer sands. Its beneficiation from primary deposits has rarely been investigated. However, there is interest in primary deposit because of the depletion of sand deposits. The Zaoyang deposit in China is the only rutile primary deposit currently mined. The plant employs a Tabling-Magnetic process which recovers only 20% Ti02 at a grade of 87%. This study shows that significant improvement on the recovery (52% at the same grade) can be achieved. This study includes a detailed mineralogical examination and the development of a processing flowsheet of the ore. The gangues are primarily amphiboles, garnets, zoisites, and chlorites. The liberation of rutile occurs at about 200 mesh. Gravitational, flotation, and magnetic separations are all employed in the process developed, depending on the mineral characteristics and experimental results. The flotations circuit utilizes benzyl arsonic acid to float rutile and sodium fluosilicate to depress the gangues. This is a new reagent scheme for rutile flotation.

Jan 1, 1989

By Pengfu Tan

A thermodynamic model and computer program, CuModel, has been developed to model the distribution behaviors of Cu, Fe, S, O, Ni, Co, Sn, Pb, Zn, As, Sb, Bi, Au and Ag, copper loss in the slag, and heat balance in copper smelting process, matte converting process and copper con-tinuous smelting process. It can be predicted for any set of controllable process parameters such as feed composition, smelting temperature, degree of oxygen enrichment and volume of oxy-gen-enriched air. This model accounts for physical entrainment between matte and slag phases. It can be used in Isasmelt process, copper flash smelting process, Mitsubishi process, P-S con-verting process and Noranda process. The predictions by the present computer model are com-pared with the known commercial data from Guixi Smelter in China, PASAR Corporation in Philippines, Horne Smelter in Canada, MIM Limited in Australia and Naoshima Smelter in Ja-pan. The agreements between the computer predictions and the commercial data are excellent. In this paper, the applications of CuModel in the copper metallurgical industries have been pre-sented. CuModel has been used by Daye Smelter and Guixi Smelter in China, and by PASAR in Philippines as well.

Jan 1, 2004

By James C. Barker

Near Rainbow Mountain in the east-central Alaska Range an ultramafic complex forms a sill-like intrusion composed of dismembered bodies exposed along the south side of the Denali Fault and Broxson Gulch Thrust. The complex comprises dunite and peridotite with lesser gabbro, which together exhibit poorly defined, steeply-dipping compositional layering. The complex hosts four types of copper-nickel occurrences which have characteristic platinum-group elements (PGE), gold, and cobalt distributions. Three of the occurrence-types are considered to have formed as a result of primary mineral segregations which developed during intrusion of the complex. The fourth type of copper-nickel occurrence formed as a result of post-magmatic hydrothermal fluids at intrusive contacts. Scanning electron microscope examination indicates that PGE occur as micron-size telluride and arsenide minerals.

Jan 1, 1987

By Mike Adams

A comprehensive pre-feasibility study has been conducted by Companhia Vale do Rio Doce CVRD) for Niquel do Vermelho nickel laterite deposit. Within this study, five integrated flowsheet options were evaluated via batch and pilot campaigns at Lakefield Oretest, over an intensive six-month period from receipt of ore to final reporting. Key technical objectives set by the client included demonstrating the technical viability of the beneficiation of several ore types, processing through integrated pressure acid leach/mixed hydroxide precipitation (PALIMI-IP) and mixed sulfide precipitation (PALIMSP) circuits, and the treatment of barren liquors to meet stringent environmental requirements. Refining of the MHP was by ammonia re-leach and solvent extraction (SX) to produce LME-grade nickel cathodes, NiCO3, NiO and CoS. LME grade nickel and cobalt was also produced by oxidation of the MSP and hydrogen reduction on the leachate. The database and data acquisition system, along with web-based reporting, enabled rapid turnaround on both daily and more comprehensive run reports, making it possible for speedy and confident decisions on operating conditions of the complex flowsheets. The high value of developing such data is emphasized and discussed as pivotal in the successful progression of laterite projects through to sustainable commercial viability. Keywords: Flowsheet, CVRD, Nickel, Piloting, Pressure, Leach, Refining.

Jan 1, 2004

By Zhang Chuanfu, Tan Pengfu

"A thermodynamic model is developed to predict the distribution behaviors of Ni, Co, Sn, Pb, Zn, As, Sb, Bi, Au and Ag in copper pyrometallurgical process. In this model, as more as 21 elements (Cu, S, Fe, Ni, Co, Sn, As, Sb, Bi, Pb, Zn, Au, Ag, 0, N, C, H, Ca, Mg, Al, and Si) and 72 compounds (in fayalite-slag-making system) or 74 compounds (in ferrite-slag-making system) are considered. Accessory-element behavior is studied for two types of slag , fayalite and ferrite, and two levels of oxidation. The allowance is also made to account for physical entrainment in the melts.-Model simulations are carried out to study the effects of controllable process parameters such as feed composition, smelting temperature, degree of oxygen enrichment and volume of oxygen enriched air. The model can be used in copper flash process, Mitsubishi process and Noranda process. The predictions by the present computer model are compared with the known industrial data from Gui Xi Smelter in China, Home Smelter in Canada and Naoshima Smelter in Japan and excellent agreement between calculations and industrial data is obtained. In this paper, the effects of oxygen enrichment, matte grade, smelting temperature, and types of slag on accessory-element behavior among matte, slag and gaseous phase have been elucidated.I . IntroductionThe presence of trace quantities of minor elements such as As, Sb and Bi in copper significantly reduces its ductility, electrical conductivity, and lowers its thermal conductivity. Embrittlement of copper also occurs due to impurity-phase precipitates at the copper grain boundary interfaces. They deteriorate not only the electrical conductivity of copper but its workability in hot working."

Jan 1, 1998

By Ragnhild E. Aune, Shahid Akhtar, Reza Beheshti

"The potential use of Black Dross (BD) as a raw material for the production of refractories, fluxing agents and glasses is the main motivation of the present study. Heat treatment experiments were carried out in Ar, and under reduced pressure (20 Pa), to evaluate the salt removal efficiency. The chemical composition of the BD after heat treatment was investigated by SEM-EDS and XRD analyses. Based on the present results, it is established that the salt starts to evaporate at ˜1273 K in Ar, and under reduced pressure. The salt removal efficiency in a 20 g sample was found to increase in both cases as a function of time and temperature. Moreover, in Ar the chlorine concentration was lowered to 0.3 wt% after heat treatment at 1523 K for 10 hours. Under reduced pressure, however, 0.2 wt% residual chlorine was obtained after 8 hours at 1473 K.IntroductionIt is believed that aluminum recycling in the near future will become the main route of aluminum production [1]. Black dross (BD) that is produced during this process contains, among other things, high amount of salts like NaCl and KCl [2, 3]. Almost 800,000 tons of BD is annually land filled in United States and this number continues to grow with the increase in aluminum recycling [2]. The BD should be dumped in controlled land field and it is costly procedure [4, 5].The water-soluble compounds in BD react with water or environmental humidity and release chlorides into the water and/or generate toxic gases such as H2, CH4, NH3 and H2 S [6-8]. In the Europe, BD is considered as toxic waste and its disposal as landfill is forbidden [8, 9]. After salt removal, the BD is considered to be non-hazardous and can be buried under ground [10].On the other hand, BD do also contains many relatively valuable compounds that may be changed in to useful materials as a result of further treatment [11, 12]"

Jan 1, 2012

By Kenneth L. Reid

The Mineral Resources Research Center at the University of Minnesota has recently installed a QEM*SEM system (Quantitative E.valuation of Materials using Scanning Electron Microscopy) to aid in detailed mineralogical evaluation of potential mineral resource developments in Minnesota and to provide services to the North American mineral industry. A primary application for the unit is to serve the Minnesota taconite industry by providing mineralogical analysis of ores and concentrator products. Minnesota taconite ores contain fine-grained magnetite in a quartz matrix. The ores undergo several size-reduction/magnetic-separation steps to produce a final concentrate with approximately 75% passing 325 mesh and containing about 5% gangue. The paper describes a typical taconite concentrator flowsheet and reports some preliminary results of the applications of QEM*SEM particle image maps and cumulative yield liberation data to samples from selected points in the concentrator circuit.

Jan 1, 1988

By Nicola Baldo, Marco Pasetto

"Recycling of tyre rubber in the road pavement, may be one of the best way to reduce waste tires in large quantities and, at the same time, improve some engineering properties of asphalt mixtures. The paper discusses the results of an experimental study, developed in order to analyse the potentialities of crumb rubber from road tyres in bituminous mixtures, using the dry process. Two types of porous asphalt mixtures and reference mixes without rubber were formulated by the traditional Marshall methodology, and mechanically evaluated by means of the Indirect Tensile Stiffness Modulus test, the Creep test (with confinement), and the Indirect Tensile Fatigue Test. Results of this study indicate that the tyre rubber has a positive influence on the performance characteristics, depending also on the grading and volumetric properties of the mix being studied: an interesting increase of the fatigue life, a better stiffness behaviour at lower temperatures and a bigger permanent deformation resistance at high temperatures are guaranteed. Introduction Recycling the rubber from used tyres, in the construction of road pavement layers, is potentially one of the more interesting and advantageous solutions from both the technical and environmental points of view, in order to reduce the total amount of car and lorry tyres to dispose. In road-building techniques, a technology, termed “wet”, for modifying bituminous binders with crumb rubber has by now become well consolidated. There have been numerous scientific studies conducted on this technology and its applications, particularly in the United States, where it has been adopted and codified in specific technical regulations (ASTM D-6114). If the wet process can be considered amply tested, the same cannot be said for a second technology, termed “dry”, which deserves careful study to evaluate its suitability and advantages. In “dry” processes, the rubber is usually used as a partial substitute of aggregate of equivalent grading and mixed with bitumen after integrating the crumb rubber in the lithic skeleton."

Jan 1, 2008

By Shoji Taniguchi, Lifeng Zhang

"In this paper, firstly the 3D single-phase turbulent steady fluid flow in a vessel with four baffles stirred by a single impeller is mathematically simulated. Turbulence is modeled by using the standard k - e model. Sliding-grid method is used to model the impeller. The flow domain is divided into two cylindrical, the inner one rotates at the same speed as the impeller, and the outer one is fixed with the baffles. Results indicate that the high-speed zone is near the paddles, and larger stirring speed generates larger fluid flow velocity. The calculated stirring intensity data are used to analyze the experimental results. Secondly the effects, such as filter pore size, gas flow rate and NaCl concentration, on bubble size are studied by experiment. For the particle removal rate by bubble flotation in this vessel, first order kinetics is adopted. The effects of initial number of the particles, gas flow rate, particle and bubble size, stirring speed and surface condition, on the removal rate constant are discussed, and an empirical equation is derived by experimental data. At last, a simple model is developed to study the particle attachment probability on bubble surface under turbulent flow conditions. IntroductionIt is well known that inclusions have a bad effect on steel quality. Trying to remove inclusions from liquid steel as many as possible is one of the main objects for the metallurgical workers. Lots of ways are developed to remove inclusions from liquid steel. Gas injection is an effective one. This technique is used to achieve homogeneity in the temperature and metal composition and to assist in the removal of second phase and dissolved impurities from molten steel. Gas injection is commonly applied to the secondary metallurgy processes and continuous casting, for example the ladle argon gas treatment, RH vacuum degassing, and the gas injection in the Submerged Entry Nozzles (SEN) of continuous casting mold, etc. The development of these processes focuses on achieving two conditions: fine bubbles and good mixing. Fine bubbles provide a large gas/liquid interfacial area and a high attachment probability to inclusions, and good mixing enhances the efficiency of impurity transfer."

Jan 1, 2000

By Dai Yongnian

The methods of treating zinc crust and its development in the last hundred years are compared and reviewed. There are better effects from normal pressure metallurgy turned into vacuum metallurgy. The traditional methods dezinc only. But we must consider that delead on further step. From lab tests to industrial scale experiment are researched. The first step-dezinc, second-delead, crude ,metal of, zinc, lead and silver are produced, The flowsheet of treating zinc crust are simplified, material consumption reduced, work condition improved, environment protect mended. This method is pointed out that its application can be expanded.

Jan 1, 1992

By H. K. Fouad, L. A. Guirguis

The starting mill strip solution· for this study· is an ammonium uranyl tricarbonate solution of pH 8.2 containing 20g uranium/liter, after a DEPA/TOPO extraction process from sulfuric acid leaching liquor. To the first portion of the concentrated acidified strip solution, hydrofuoric acid is added at 95°C in reduced condition to obtain uranium tetrafluoride. The second portion of the uranyl carbonate strip is subjected to a precipitation step by admixing 0.3 volume of non-solvent precipitating agent such as acetone per volume of uranium. ·Uranium oxide (U30 8) is obtained from this precipitate by calcination for half an hour at 800°C in air. The third portion of the strip solution is neutralized to a pH 6.5 with sulfuric acid to precipitate iron and other contaminants. The solution is further acidified to a pH 1.85 with continuous air bubbling to remove CO2, followed by H2Ch precipitation at pH 3.5 to obtain uranyl peroxide. The latter is reduced by stannous chloride to obtain uranium trioxide dihydrate UO3. 2H20. Identifications, characterization· and purity of these products are carried out by complete chemical analyses, Scanning electron microscope study, tap density determination, X-ray diffraction and infrared spectroscopic investigations. The achieved results agreed well with that of the published data for these nuclear grade purity products.

Jan 1, 2000

By Taufiq Hidayat

Accurate description of complex phase equilibria provide the foundations for the improvement of non-ferrous pyrometallurgical smelting and recycling processes. Recent advances in microanalysis and experimental techniques enable accurate phase equilibria characterisation. Quantitative microanalytical techniques including Electron Probe X-ray Microanalysis and Laser Ablation ICP-MS enable the concentrations of major and minor elements present in different phases in samples to be accurately measured providing data that cannot be obtained using bulk chemical analysis techniques. High-temperature equilibration experiments coupled with the subsequent analysis of elementary reactions at micro- and macro-scales ensure the attainment of equilibrium conditions, and therefore, ensure true phase equilibria information is obtained. Examples of the application of the improved methodology on the investigation of phase equilibria of low-order and complex, multi-component gas/slag/matte/metal/solids Cu2O–PbO–ZnO–Al2O3–CaO–MgO– FeO–Fe2O3–SiO2–S systems and the distribution of minor element are provided. The experimental study is closely integrated with thermodynamic database development for the above system. Example of implementation of the research outcomes into industrial operations is demonstrated.

By Ryosuke Matsuoka

Keywords: Tantalum capacitor, Scrap, Recovery, Titanium, Chlorination A recycling process for tantalum from capacitor scraps using an oxidation process followed by mechanical separation and chemical treatment was investigated. This study demonstrates that sintered tantalum electrodes inside the capacitor scraps can be mechanically collected after the oxidation of the scraps in air, and high-purity tantalum oxide powder (Ta2O5) was efficiently recovered after chemical treatment. By reducing the Ta2O5 obtained through magnesiothermic reduction, tantalum powder with 99 mass-% purity was obtained. Using the chlorination for tantalum recovery was also investigated, and the tantalum or tantalum compounds were reacted with chloride wastes such as FeClx. It was found that tantalum was effectively separated and purified when tantalum powder is reacted with FeClx at 1100 K under an argon atmosphere. This recycling process utilizing chloride scrap has now been extended to other reactive metals such as titanium.

Jan 1, 2004