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By G. B. Harris

Jaguar Nickel Inc. is developing the Sechol Nickel-Cobalt Laterite Project in Guatemala, Central America. Recognizing the potential advantages offered by chloride brine chemistry, Jaguar, at the facilities of Process Research ORTECH Inc, Mississauga, has developed an Atmospheric Chloride Leaching Process using a mixed chloride lixiviant to recover the nickel and cobalt, whilst leaving the majority of the iron and magnesium in the leach residue. Subsequent solution purification and mixed nickel/cobalt hydroxide product recovery is by standard precipitation methods, using recycled caustic magnesia, with a final stage of pyrohydrolysis of a portion of the concentrated magnesium chloride brine for recycling both the caustic magnesia and chloride lixiviant. The flowsheet that has been developed also offers opportunities for by-product recovery and efficient, environmentally clean process effluent management. The paper discusses some of the early leaching results in the context of strong chloride brine chemistry, with emphasis on how the controlling of water activity, hydrogen ion activity and chloride concentration permits the selective leaching of nickel and cobalt from an iron-magnesium matrix. Keywords: nickel, cobalt, iron, magnesium, Sechol, Guatemala, chloride, pyrohydrolysis

Jan 1, 2004

By Rolando Campos

Until 1970, the Caletones Smelter of CODELCO-CHILE, División El Teniente, operated under the conventional pyrometallurgical process used by most of copper smelters. The annual copper production varied around 165.000 tons. The failure in the commissioning of the "oxygen smelting" technology in Peirce- Smith converters (1970-1972), forced further introduction of transcendental changes in the Caletones smelter operating scheme. Implemented technological innovations were based on wide studies and research works performed by División El Teniente. This paper presents a summary of technological modifications introduced, their impact on production and energetic performances, and short and medium terms improvement plans.

Jan 1, 1993

By W. H. (Bill) Jay

The destruction of cyanide creates a significant impost on the financial returns of gold mines. These losses increase substantially when ores containing cyanide-soluble copper are treated. Failure to remove or destroy free or WAD cyanide before it is discharged into tailings dams has, on a number of occasions, led to significant fish, bird and animal deaths. Thus, the retention of cyanide within the leach circuit and the recovery or removal of stable metal cyanide complexes needs to become standard practice for all gold mining operations. Furthermore, reducing cyanide purchases will minimise the quantity of cyanide transported to the mine site thereby reducing the opportunity for spillage of this chemical. Many different physical and chemical methods have been investigated for the removal of cyanide from process solutions. All cyanide destruction methods create a financial impost on the economic viability of the gold mine. To reduce these costs, the recycle of cyanide and the economic recovery of the metals solubilised by cyanide is of prime importance. The alternative methods currently in use, or under consideration for the treatment of copper cyanide, entail high reagent costs, produce the recovered metal in a contaminated form and require the safe handling of hydrogen cyanide. These processes will be briefly discussed within this report Environmental and financial benefits are enhanced by recent laboratory and pilot plant studies conducted by Oretek Limited. The Oretek CPC process for the recovery of copper and the recycle of cyanide from copper cyanide-containing solutions does not require pH adjustment to the alkaline cyanide leach conditions. Copper ions are coordinated to a water-soluble and/or an organic soluble polychelating agent under alkaline conditions and the cyanide ions are displaced Membrane separation, or phase separation of the polychelated copper from the cyanide ions enables the cyanide ions to be recycled and the copper to be directly electrowon from the polychelating polymer. The polychelating polymer is then recycled. Ion exchange resins and solvent extraction systems which may be incorporated into the above process will also be discussed in detail.

Jan 1, 1998

By Y. Yang, S. Peelman, J. Sietsma, Z. H. I. Sun

The rare earth elements (REEs) present in the Kiruna iron ore mine tailings are being considered as a new REE resource for the EU. These tailings, after beneficiation, contain approximately 5000 ppm of rare earths, concentrated in apatite and monazite minerals. To economically extract the REEs from these tailings the phosphorous contained within the apatite must also be extracted and the waste production of the process should be minimal. To achieve the extraction of REEs and phosphorous HCl and HNO3 were investigated as possible leaching agents. Based on the results a leaching process using HNO3 is proposed. This process produces H3PO4 from the apatite while simultaneously dissolving the REEs. The resulting leach liquor is then cooled to remove the unwanted Ca as Ca(NO3)2. Analysis of the leach liquor reveals extraction ratios of between 75% and 100% for the heavy REE (e.g. Y, Eu, Dy, …) and below 40% from the light REEs (i.e. Ce, La). Full phosphorous extraction was also achieved.

Jan 1, 2016

By N. Tsuchida

Sumitomo Metal Mining Co. Ltd. (SMMC) is currently developing the flowsheet to treat stockpiled limonite, a type of laterite ore, at Rio Tuba on southern Palawan Island, Philippines. The new plant will be commissioned at the end of 2004. Rio Tuba Nickel Mining Corporation (RTNMC) has been mining saprolite since 1977, and the limonite ore located above the saprolite ore body has been stockpiled separately according to nickel and magnesium content. Ore from these stockpiles will be blended and used for the operation. The annual production of nickel will be 10,000 metric tons for the next twenty years. The proposed process consists of ore preparation, high pressure acid leach (HPAL), counter- current decantation wash, impurity removal and sulfide precipitation. Precipitated mixed sulfide will be processed to electrolytic nickel by the Matte Chlorine Leach Electrowinning (MCLE) process at Niihama, Japan. SMMC has established new technologies during the process development, such as zinc removal and sulfide precipitation. Applying this technology, preferential removal of zinc can be achieved by hydrogen sulfide gas with negligible loss of nickel. Precipitation of nickel by hydrogen sulfide gas is carried out at low temperature. Slow kinetics is selected for control of the particle size of the precipitated mixed sulfide. Keywords: HPAL, Zinc Removal, MS Production

Jan 1, 2004

By Sharif Jahanshahi

Calcium ferrite slags are often associated with Professor Yazawa due to his pioneering work on the thermodynamics of this type of melts. Over the past years CSIRO has invested some effort in studying physico-chemical properties of such melts to fill in some gaps in our knowledge and explore opportunities for application of the understanding developed. These investigations cover thermodynamics, transport properties of calcium ferrite based slags, as well as the kinetics of reactions of such slags with refractories. The present paper provides an overview of some of these studies and highlights some of the interesting behavior of such melts. The oxidation state of copper and arsenic in calcium ferrite based slags are predominantly Cu+ and As3+, respectively, at oxygen potentials below 10.1 atm. The concentration ofCu2+ in such slags becomes significant at oxygen potentials of greater than 10'1 atm at 1300 ?C. The activities of CuOo.s and AsOl.S in calcium ferrite slags show strong deviations from the Raoultian Law, while that of CoO is very close to ideal behaviour with respect to pure solid CoO. Addition of Si02 to calcium ferrite slags can have significant effects on the activities of FeO and Fe2O3 and hence the stability of magnetite phase. Transfer of oxygen in calcium ferrite slags is fast with diffusivity of 2xlO?3 cm2/s at 1350 °C and activation energy of 16 kcal/mol Presence of solid phases, such as magnetite, has pronounced effect on the viscosity of calcium ferrite slags. The observed dependence on solid loading and shear rate indicates deviation from Newtonian behaviour. The interfacial tension between copper mattes and calcium ferrite slags is strongly dependent on the matte grade, with the determined values being much lower than the corresponding ones for interfacial tension between similar mattes and iron silicate slags. MgO, Cr2O3 and MgCr2O4 have low solubility in calcium ferrite slags and their solubility increases with increasing copper oxide content of the slag at 1300 °c. The oxidation state of the slag has strong effects on phase transformation, dissolution rate and disintegration of refractories in calcium ferrite slags. Other key factors with major impact on slag-refractory interactions include viscosity and surface tension of slags as well as the contact angle between slag and refractory material.

Jan 1, 2003

By Takao Yasugi

The majority of copper in the raw material migrates to the de-copperized dross that forms when the crude lead produced in the blast furnace is treated in the de-copperizing process. The de-copperized dross is treated in the electric furnace producing matte, speiss, and crude lead. The de-copperized dross also contains the silver. Therefore, it is important to improve the rate of silver migration to the crude lead. For this reason, the behavior of silver between the matte, speiss and crude lead phases was examined. At the same time, several tests to improve the percentage of silver migrating to crude lead were conducted.

Jan 1, 2003

By Rodney L. Williamson

Optimal estimation theory has been applied to the problem of estimating process variables during vacuum arc remelting (V AR), a process widely used in the specialty metals industry to cast large ingots of segregation sensitive and/or reactive metal alloys. Four state variables were used to develop a simple state-space model of the V AR process: electrode gap (G), electrode mass (M), electrode position (X) and electrode melting rate (R). The optimal estimator consists of a Kalman filter that incorporates the model and uses electrode feed rate and measurement based estimates of G, M and X to produce optimal estimates of all four state variables. Simulations show that the filter provides estimates that have error variances between one and three orders-of-magnitude less than estimates based solely on measurements. Examples are presented that verify this for electrode gap, an extremely important control parameter for the process.

Jan 1, 2001

By A. A. el-Geassy

High-grade iron ore fines rejected from the DRl plants (>96%Fe20) were isothermally reduced in 30-60%COIH2 gas mixtures at 973-1273K. The freshly reduced reaction products were then subsequently carburised in either H2/CO or H2/CO/S mixtures at 823-1073K for 30-120 min. The thermogarvimetric technique was used to follow up both of reduction and carburisation reactions as a function of time. The carburised samples were characterized by X-ray and Mossbauer techniques. Chemical and carbon analyses were also applied. The influence of temperature and gas composition on the reduction behavior was investigated. The calculated values of apparent activation energy, application of gas-solid mathematical formulations were correlated with the microstructures to predict the reduction mechanism, The influence of carburization time, temperature, CO contents in H2/CO or H2/CO/S were investigated. A conversion extent of Fe to Fe3C was taken as a measurable index for the efficiency of carburization reaction under the different experimental conditions.

Jan 1, 2003

By Young-Geun Park

A new decarburization model for the RH system was constructed for calculating the decarburization reaction using a three-dimensional fluid dynamics program. The entire fluid flow in the RH process was calculated by evaluating the shape and volume of the plume zone, formed by Ar gas blown through multiple nozzles on the wall of the snorkel. On the basis of this fluid flow, the decarburizaiton reaction was calculated through establishing the decarburization reaction model, which considers the thermodynamics, reaction kinetics, and the decarburization sites (Ar bubble surface, bath surface, and the CO bubble fomtation at inner sites). The results from this model were compared with a real RH operation results with good agreement. Because it is possible to predict the carbon concentration at various conditions using this model, it may be useful in increasing the decarburizaiton rate. Key words : RH process, plume zone, decarburization, Ar bubble surface, bath surface, inner site, circulation flow rate.

Jan 1, 2001

By S. E. Khalafalla

A method for preparing ferrochromium alloys containing less than 2 pct carbon has been devised in a single vacuum furnace reactor. This method can conserve chromium and should reduce the capital and energy requirements relative to chromite electrothermal reduction. Reduced products containing less than 2 and as low as 0.01 wt pct carbon were obtained by reacting pellets of chromite and carbonaceous reductant mixtures at pressures of 0.1 to 1 ton and temperatures of 1,230° to 1,320° C. The extent of reduction increased with increased temperature and decreased pressure; however, operating conditions were limited due to the onset of significant chromium vaporization at higher temperatures and lower pressures. Foundry coke, anthracite, and carbon black were found to be superior to graphite as reductants. The reduction of chromite to metallics was found to proceed via the carbide intermediates Fe3C or Cr3C2. Lime accelerates the. rate of solid state reduction of chromite and can shorten the furnacin1r time at 1,3000 C under vacuum from 13 hours to less than three hours. Additional lime and silica are added to the hot reduced chromite after releasing the vacuum and raising the furnace. temperature to 1, 700° C. Soaking the charge for about 20 minutes gave a button of low carbon ferrochromium alloy beneath a well-defined slag layer.

Jan 1, 1985

By J. V. Atwood

The U.S. Bureau of Mines has developed a novel Double Membrane Electrolytic Cell (DMEC) that exhibits unique features for recycling contaminated metals and metal alloys. The DMEC incorporates two anionic ion exchange membranes, separating anodic and cathodic regions of the cell. The ion exchange membranes prevent significant transport of unwanted cationic impurities to the catholyte from the impure anolyte while the anion/cation balance in cell compartments is maintained through the free movement of anions between compartments. The membrane barrier makes it possible to electro refine highly contaminated materials or to electrowin from solution while utilizing alternate anode reactions. Sinceanolyte and catholyte cross contamination has been eliminated, premium cathode products are produced. The DMEC has been tested at bench, pilot, and commercial scales. Configuration of the DMEC, cell operation, scale, up efforts, and significant design factors are discussed. Two separate recycling investigations utilizing DMEC technology are presented. The first investigation examines recovery of high purity cobalt and nickel from severely contaminated super aIloy scrap. The second involves? upgrading contaminated cobalt in the U.S. Government's National Defense Stockpile. Capital and operating costs for both potential applications are presented.

Jan 1, 1995

By M. Rubinstein, N. C. Koon, B. N. Das, V. G. Harris

"Copper and gold - based alloys having giant magnetoresistance properties were produced by melt spinning from arc melted and cast rods. The ribbon width varied between 1 and 2 mm and the ribbon thicknesses were in the range of 30 to 50 11m. The uniform microstructure of the cast rods indicated the composition homogeneity in the starting material. The ribbons showed composition uniformity across the cross section from EDX analysis. However, the spun ribbon microstructure changed from a 'frozen in' region near the wheel side to a nanosize spherically precipitated phase towards the freely frozen surface. The evolution of the microstructure from the spun ribbon state to the annealed ones was studied by optical microscopy, SEM and TEM. The structural information of the spun and annealed specimens was obtained from X - ray, electron diffraction, electron microscopy and ferromagnetic resonance. Magnetoresistance was measured by the four point probe method.IntroductionRecently. Giant Magnetoresistance. GMR. has been observed in sputtered thin films alloys of Ag. Au and Cu with Co and Fe [1. 2. 3]. The sputtered films are produced by condensation of the alloys from the vapor phase. These Ag. Au and Cu alloys are miscible and homogeneous in the vapor and liquid phase (except Ag alloys which exhibit phase separation even in the liquid phase) but immiscible and heterogeneous in the solid phase. In our work we have produced thin ribbons of the Cu and Au alloys about 30 µm thick from the miscible state in liquid phase by rapid solidification melt spinning. The microstructural development of the ribbons was investigated in the as - spun condition and on annealing. The other properties such as magnetization. GMR and Mossbauer Spectroscopy were also investigated in the various microstructural conditions of the ribbons."

Jan 1, 1994

By Zhendong Tao, Wei Huang, Zhongxi Yang, Hang Guo, Haoran Geng, Jingxiang Yao

"CaSO3.0.5H2O typed Flue Gas Desulfurization (FGD) gypsum is a by-product formed in flue gas desulfuration by double-cycle fluid bed method, its composition is different remarkably from that of gypsum yield by normal desulfuration methods, and few studies using it as cement retarder have been carried out. In this paper, the experimental study using CaSO3•0.5H2O typed FGD gypsum as cement retarder was carried out. The experimental results indicate that, when FGD gypsum is added solely into cement, the retarding action is not satisfactory because of its slow dissolution rate; The composite retarder composed of FGD gypsum and natural gypsum can regulate efficiently setting time of cement over a wide range of addition and rate of both each other, and the mechanical property of cement can be improved significantly.Fire-power plants have discharged a lot of harmful gases such as SO2 etc., which has resulted in serious pollution on the environment. To reduce harmful gas containing sulfur in the flue gas, various flue gas desulfuration (FGD) techniques have been developed. At present, the FGD method used widely is to add desulfuration agents such as limestone powder or other calcareous-contained materials during the coal burning or in the flue gas so that the components containing sulfur react with them to form solid sulfate or sulfite and to be separated from the flue gas by collectors. CaSO3•0.5H2O and CaSO4•2H2O typed FGDgypsum can be obtained respectively by dry and wet FGD process[1,2]. As a by-product of fire-power plant, features of of FGD gypsum and its applications have been paid great attention. Pavel Tesa'rek et al [3] presented in full the characters and properties of FGD gypsum; Zofia Konik et al[4] prepared expansive additive used to cemnent industry by using FGD gypsum and aluminate clinker; A. K. Alva et al [5] investigated the effects of FGD gypsum and fly ash on soil properties and found the growth of seedlings of either rootstock improved significantly in soils amended with FGD gypsum and fly ash. FGD gypsum also can be used in gypsum binders, plasters and plasterboard manufacture [2.6]. C. S. Poon et al [7] investigated the effects of FGD sludge on the pozzolanic reaction of reject-fly-ash-blended cement pastes. Many studies using CaSO4•2H2O typed FGD gypsum as cement retarder has been reported[2,8-12]. Howevere, few studies using FGDG as retarder were reported so far. In present study, the chemical compositon, phase composition, structure and features of CaSO3•0.5H2O typed FGD gypsum have been analyzed, and its application characters used as cement retarder have been investigated experimentally."

Jan 1, 2008

By Eliezer Martinez-Jimenez, Gretchen T. Lapidus

"Electro-assisted reduction is an effective pretreatment to render chalcopyrite less refractory towards oxidative leaching. In this process, chalcopyrite is selectively converted to chalcocite or copper metal in an electrolytic cell under ambient conditions, while ferrous ion is leached into solution. However, the reaction velocity is hampered by the formation of a ferrous sulfide passivating layer on the solid surface, especially at elevated solid to liquid ratios. In the present work, several strategies for overcoming this problem were evaluated. On one hand, specific ligands for ferrous ion were added in order to increase its solubility and, on the other, an anode material which promotes the oxidation of the sulfide ion was chosen. Leaching tests showed citric acid to be an effective ligand for both ferrous and ferric ions and, in combination with a lead-silver anode, significantly increased the kinetics of chalcopyrite reduction and subsequent copper leaching.IntroductionAttempts to oxidize chalcopyrite at a rapid rate in aqueous solutions, below their normal boiling point, have met with difficulties because of passivation by some of its own components. An alternative line of research explores reductive pretreatment, transforming the chalcopyrite into less refractory copper phases, which can later be oxidized. A recompilation of these efforts up until 2000 was published by Dreisinger and Abed [1]. However, this practice usually requires large excesses of reducing agents, such as copper, lead, aluminum or iron, and in this last case at near-boiling temperatures, in highly"

Jan 1, 2012

By John O. Burckle

For years, the measurement of fugitive emissions from the primary copper converter has defied all attempts based on inferential measurements, It has been concluded by virtually all investigators that the only dependable tech¬nique to measure these emissions would be to completely enclose an operating converter to permit the capture and measurement of all emissions. However, complete enclosure with a metal hood is difficult; many of the most serious fugitive emissions result during periods when the converter must be attended with crane-operated equipment. This approach would require either opening of the enclosure to permit the entry of large items of equipment or completely new methods for charging and tapping converters' The installation of the air curtain hooding system at ASARCO's Tacoma smelter has permitted a quantitative approach to the direct measurement of the fugitive for the first time. In this program, the fugitives captured by the air curtain were measured at a downstream sampling point in the exhaust side of the air curtain system during the various portions of the converter cycle. Emission factors were established for sulfur dioxide, filterable particulate (method 5), inhalable particulate, and selected trace elements.

Jan 1, 1983

By Godwin J. Igwe

For soil remediation technology to be effective, a thorough understanding of the interactions between a targeted contaminant and the soil matrix is crucial. Proper selection of remediation technology, based on understanding the bonding/binding characteristics of the soil and contaminant, can often result in significant remediation cost savings. Contaminated soil cleanup is complicated by both the physical nature of the soil formation and the behavior of contaminants introduced into the formation. Contaminants can exist in the subsurface in different phase attached to the soil surfaces, dissolved in the ground water, or occupying pore spaces as a separate gaseous or liquid phase. Contaminants properties and how they exist in the subsurface influence their toxicity, mobility and treatability with different remediation technologies A soil characterization study was performed to provide information for remediation technology selection for an inorganic lead contaminated soil. The soil pH, TCLP analysis, thermogravimetric analysis, the soluble anions and cations present, equilibrium leaching tests, analysis by x-ray fluorescence, sequential extractions and speciation analysis using scanning electron microscopy, were all used. Results provided many insights into contaminant behavior in the soil, indicating ultimately whether soil washing or solidification/ stabilization remediation technologies were applicable.

Jan 1, 1994

By Yusuke Kimura, Ken-ichi Yamaguchi

"Secondary materials have long been processed at the S-furnace of the Mitsubishi continuous copper smelting and converting process at Naoshima Smelter and Refinery. Intensive recycling in the recent years has formed concerns that impurities in the secondary materials may cause drastic changes in the chemical properties of the CL-slag, which is separated from matte in the smelting stage. Among various impurities included in secondary materials, the authors have studied the influences of sodium oxides in the CL-slag because the behavior of sodium oxide has scarcely been studied with respect to the copper smelting slag. The examinations have been applied experimentally on the distribution between slag and matte of arsenic whose acidic characteristics suggest strong affinity to sodium-oxide of basic characteristics in silicate melts. The results have been discussed by thermodynamic evaluations and the results of pyro-tests at the commercial furnace.IntroductionAt Naoshima Smelter and Refinery, the existing line of the Mitsubishi continuous copper smelting and converting process has been operated since 1991. The Mitsubishi Process consists of three furnaces namely the S-, CL- and C-furnace as shown in Figure 1. In the S-furnace, copper concentrate and powdery secondary materials (scraps, sludges, etc) are charged through the top lances with oxygen enriched air. The other secondary materials of lumpy shapes are charged through the chute installed on the furnace roof. Charged materials are smelted by the reaction heat in accordance with the oxidization of copper concentrate. The mixed melt of matte and slag overflows through the launder into the CL-furnace, where the melt is separated into slag and matte by the difference of their specific gravity. Matte is siphoned out and sent to the C-furnace and converted to blister copper continuously. The CL-slag overflows continuously through the slag outlet to be water-granulated. Granulated slag is sold as a raw material used for the cement production and so on. Various secondary materials have been processed at the S-furnace of Naoshima Smelter and Refinery. Intensive recycling in the recent years has formed concerns that the chemical properties of the CL-slag may change drastically due to impurities originating from secondary materials. Among various impurities included in secondary materials, the authors have studied the influence of sodium oxide in the CL-slag because the impact of sodium oxide has scarcely been studied with respect to the copper smelting slag. The examinations have been applied experimentally on the distribution between slag and matte of arsenic whose acidic characteristics suggest strong affinity to sodium-oxide of basic characteristics in silicate melts."

Jan 1, 2012

By G. R. Palmer

The success of future electric vehicles will depend greatly upon the power supply choices made today. Research is presently being conducted by automotive engineers and electrochemists to determine what battery type may be the most promising. Not only are product production and application efficiencies being evaluated but also environmental concerns of reclamation and recycling. Rechargeable batteries using nickel-metal hydride electrodes are strong candidates for these electric vehicle applications. The U.S. Bureau of Mines is investigating hydrometallurgical technology that separates and recovers purified metallic components present in nickel-metal hydride battery scrap. Sulfuric, hydrochloric, and nitric acids are all capable of dissolving the battery electrode alloys given the proper operating conditions. Solvent extraction of the leach solutions using D2EHPA removes iron, and selective precipitation shows promise of recovering the other metals in the H2SO4 and HNO, systems.

Jan 1, 1994

By Derk G. E. Kerfoot

The extractive metallurgy of nickel and cobalt has proved to be a particularly fruitful area for innovation in hydrometallurgy and electrometallurgy ever since the development of the Hybinette process for nickel in the early 1900's. In current practice, nickel concentrates are generally smelted to high grade mattes which are then refined to metal by a combination of hydrometallurgy and electrometallurgy, although low grade copper-nickel concentrates are refined directly by the ammonia pressure leach process. Matte refining processes in commercial operation include the direct electrolysis of matte, the ammonia pressure leach, sulphuric acid leaching using air or oxygen at elevated pressure, or at ambient pressure, and chlorine or chloride leaching. Refined nickel is recovered either as electrolytic cathode, or as metal powder by hydrogen, reduction. Hydrometallurgy has also found application in the treatment of nickel laterite ores, both in the reduction roast ammonia-ammonium carbonate leach process, pioneered by Caron and in the Moa Bay acid leach process. Cobalt is recovered as a co-product of copper in central Africa, and as a byproduct of hydrometallurgical nickel refining elsewhere. In the African plants, the copper-cobalt concentrates are roasted and leached in sulphuric acid solution, and copper and cobalt are recovered separately from the leach solution by direct electrowinning. A variety of hydrometallurgical techniques are used for the separation of cobalt from nickel, including selective precipitation and crystallization, solvent extraction, and ion exchange. Like nickel, refined cobalt is recovered either as electrolytic cathode or as metal powder by hydrogen reduction.

Jan 1, 1988