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By L. Becze, S. J. Hock, G. P. Demopoulos

"Regeneration of HCl from chloride solutions is commercially practiced by high temperature (800-900 °C) pyrohydrolysis associated with high energy consumption and capital cost. As an alternative to pyrohydrolysis a novel low temperature ( <200 °C) non-autoclave hydrolytic process has been studied in this research work, which comprises two steps. In the first step, ferrous chloride is oxidized by oxygen at 1;150 °C, followed by hydrolytic decomposition of ferric chloride to coarse hematite particles and superazeotropic hydrochloric acid (8-9M) operated at approximately 180 °C. This paper provides a summary of the laboratory results related to both oxidation and hydrolysis and presents a newly designed conceptual process flowsheet.IntroductionRecovery of base, noble and rare metals from ores and secondary materials (slags, dusts, residues) by chloride-based hydrometallurgical processes holds a lot of promise if a low cost HCl process becomes available. This is particularly so due to the high activity of HCl or more accurately activity of hydrogen ion [1] in concentrated chloride media and the formation of chlorocomplexes allowing for effective leaching under atmospheric leaching conditions and simultaneous ease of metal separation. However, during leaching significant amount of iron, which is associated with most of ores and secondary materials, goes into the solution. Hence, the obtained leach solution has to be treated to convert iron chlorides into easily filterable iron oxide and simultaneously produce concentrated hydrochloric acid. Apparently the critical operation of these processes is the regeneration of the lixiviant (HCl). Currently in the industry, its regeneration is accomplished by high capital and intensive pyrohydrolysis which operates at 700- 900 °C. Aimed at lowering the operational cost of pyrohydrolysis a process called PORI [2] was developed and tested in pilot plant scale in the 1970s for the purpose of treatment of pickle liquors without, however, resulting in industrial application."

Jan 1, 2011

By Maria Cristina Ruiz

The removal of iron from the leaching circuits is a common problem in the hydrometallurgical processing of non ferrous metals. Among the currently available processes, hematite precipitation is the most recommendable from an environmental point of view. This paper is concerned with the batch precipitation of hematite from ferrous sulfate solutions. One of the main objectives of the study was to determine the effect of the experimental conditions on the extent of iron precipitation as well as the purity and the particle size distribution of the precipitates. The main variables studied were temperature (180 to 220 ºC), concentration of sulfuric acid (1 to 10 gpl), initial iron concentration (1 to 15 gpl) and partial pressure of oxygen (3 to 7 atm). The results showed that increasing the oxygen partial pressure from 3 to 7 atm produced a very small increase on the rate of hematite precipitation indicating that a large partial pressure of oxygen is not needed for an effective ferrous to ferric oxidation. An increase in the temperature produced finer precipitates with lower sulfur contents. On the other hand, an increase in sulfuric acid concentration and initial iron concentration produced precipitates with larger particle sizes and higher sulfur contents.

Jan 1, 2006

By S. Djaroudib

Keywords: iron recovery, hematite, hydrolysis, polyvinylpyridine The precipitation of hematite (Fe2O3) from ferric chloride media at ambient pressure and at temperatures below 100°C was studied as part of a program to recover a marketable iron product form metallurgical processing streams and effluents. Hematite was formed in preference to ferric oxyhydroxides (e.g. ß-FeO?OH) by controlling the precipitation conditions, especially by adding Fe2O3 seeds. The extent of the hydrolysis reaction was found to depend primarily on temperature and on the free-acid concentration. As to the latter, the controlled addition of an adsorbent of free acid, in our case the anionic resin polyvinylpyridine (PVP), was shown to allow for the nearly complete removal of iron as readily filterable Fe2O3. The hematite product typically contains = 63% Fe and = 1.5% Cl, and its composition does not change appreciably upon repeated cycling using regenerated PVP.

Jan 1, 2005

By K. Östcrdahl

We are developing a cost-saving and environmentally friendly process with low energy consumption to recover the metal content and recycle the acid from spent pickle baths. The metals are precipitated as metal fluorides, which can be turned into metal oxides and hydrofluoric acid by thermal hydrolysis. In the proposed process the solution is concentrated by nanofiltration and the metals are precipitated in a subsequent crystallization step. Different nanofiltration membranes have been evaluated in experimental batch tests. The membrane MPF-34 from Koch Membrane Systems offered both good flux and acceptable metal retention even after long periods of acid storage. The solubility of B-FeF3.3H20 has been measured at varying acid concentrations and at different temperatures. The solubility decreases with increasing hydrofluoric acid and nitric acid concentrations. This suggests that the crystallization process should be operated at high acid concentrations. The crystal growth rate of B-FeF3.3H2O is found to be quite low but increases significantly with temperature. This suggests that the crystallization process should be operated at higher temperatures (40 - 60°C). Within the project a pilot plant has been constructed where the spent pickle bath solution is concentrated by nanofiltration to the desired metal fluoride supersaturation, and B-FeF3.3H2O is crystallized in a 10 L continuous crystallizer.

Jan 1, 2006

By D. M. Muir

Many plants produce iron(II)/(III) waste liquors which must be treated by neutralisation and precipitation to remove the iron. Iron can be precipitated as crystalline goethite or jarosite by controlled oxidation at low pH and as magnetite by controlled oxidation at high pH, but only at elevated temperatures (>70°C). This study focuses on the characterisation and settling properties of the iron oxides produced at ambient temperatures using various neutralising agents in order to improve the performance of thickeners. It was found that two-stage addition of caustic to FeC12 solutions produced a fast settling material characterised by Mossbauer spectroscopy and XRD as maghemite and magnetite. However, lime and magnesia additions resulted in more ferrihydrite formation and much lower settling rates because of the enhanced oxidation of Fe(II) by air. Settling rates decreased significantly as the proportion of Fe(III) to Fe(II) in the liquor increased. The mechanism of iron oxide precipitation is discussed together with some reasons for the different behaviour of the neutralising agents.

Jan 1, 2006

By G. L. Oldright

As sponge iron is much like porous, coarse sand, it is a tempting material to use in place of coarse scrap iron as a precipitant of metals, for scrap iron is relatively awkward to handle and exposes only a small amount of surface to pregnant solutions. The results of the experiments described in this bulletin are largely a record of the behavior of sponge iron as a precipitant of lead and copper under laboratory conditions comparable to those that would obtain in a commercial plant were it attempted to secure the maximum contact of surface between solution and precipitant. Physically, the study is largely one of the rates of diffusion of the metal ions in the solutions and through the metallic coatings surrounding the sponge iron particles. The practical objectives are to remove completely the valuable metals from solution and at the same time to obtain a precipitate of good grade. In order to fulfill this latter requirement, the precipitant should be almost completely consumed. These practical ends are usually secured by having the two substances involved pass each other counter-currently-that is, in such a manner as to have the strongest precipitant in contact with the most impoverished solution, and vice versa. EXPERIMENTS WITH LEAD SOLUTIONS In nearly all of the schemes involving the leaching of lead from its ores the metal has been put into solution as the chloride, and fairly concentrated liquors have been employed. The solubility of lead under such conditions is comparatively small at best; the hot pregnant liquors from which the metal is to be precipitated are then made nearly saturated with respect to lead, and only a very small amount of acid is used. Therefore it was not as necessary to learn the behavior of the sponge iron in precipitating lead from solutions of widely differing composition as to learn under what conditions, and with what mechanisms, this precipitation might be carried out most readily.

Jan 1, 1928

The preeipitation of dissolved lead from a strong brine by metallic iron is a chemically controlled, first order reaction. The precipitation rate is sensitive to changes in chloride concentration and temperature. The precipitation of dissolved silver is a diffusion controlled, first order reaction. The precipitation rate is insensitive to changes in chloride concentration and temperature.INTRODUCTIONLead and silver sulphates can be extracted from electrolytic zinc plant tailings, or residues, by leaching with strong brine solutions, the lead and silver going into solution as complex chlorides. One of the methods which can then be used to recover the dissolved lead and silver is to precipitate them with metallic iron. The deposition reactions which take place are of the type Pb++ Fe - Fe++ Pb............ (a)To fit such a method of precipitation successfully into a practical flowsheet it is necessary to have some knowledge of the kinetics of the various reactions, Le. to know how the precipitation rates vary with temperature, brine and metal concentrations, and so on. Reaction rates are also needed to design suitable precipitation vessels. However, when examining the possibility of using a brine leaching process to extract the lead and silver from the residue produced at the Risdon plant of the Electrolytic Zinc Co. of Australasia, it was found that, although the use of metallic iron to recover lead and silver from the pregnant brine had been reported by Ralston (1924) and by TrumbulI, Hardiek and Lawford (1948), very little was known about the precipitation reactions. Consequently a laboratory investigation was undertaken, and this paper covers those aspects considered to be...

Jan 1, 1961

By João Queiroz, Cristian Marquez-Sarmiento, Luiz Teixeira

The removal of various metals from process waters and effluents is usually done by precipitation of the corresponding hydroxide. Manganese however is one metal that does not respond efficiently to that approach. It may be seen in its eH X pH diagram that the way of oxidation to Mn IV rather than hydrolytic precipitation of the Mn II ion as its hydroxide, is the way to efficient precipitation of Mn in the pH range 6 to 10. We studied the use of oxidants O2; NaClO; H2O2; Caro´s Acid (H2SO5) and the combinations of O2 or H2O2 with Na2S2O5, and H2O2 with NaClO, for the oxidative precipitation of Mn from synthetic solutions starting with 10 mg/L Mn, at 25 oC. In adequate conditions, which include pH > 8, it is possible to reach final [Mn] less than 0.1 mg/L in 60 minutes of reaction time.

Jan 1, 2014

By Bratt G. C, Horsham T. R, Langlois D. R

Mercury is precipitated from weakly acidic sulphuric acid plant waste liquor at the Risdon Works of the Electrolytic Zinc Company of Australasia Limited. Factors determining the choice of process and reagent, as well as details of process development including scale- up, and the time scale of implementation are outlined. The plant is designed for a maximum flow of 120 m3/h.of liquor containing mercury and saturated with sulphur dioxide. Mercury is precipitated by fluidised beds of aluminium pellets contained in lead columns. Liquor is then clarified with plate and frame presses. Experimental work on the mercury precip- itation reaction was conducted in three phases involving a scale-up of 100 times in equipment size. Extensive pilot filtration work was carried out on a 1 m2 press. Scale-up of 120 times was required for specification of plant filters. The basis of scale-up is outlined.

Jan 1, 1977

By F. A. Schaufelberger

Early work on chemical precipitation of metals from metal salt solutions is reviewed. The chemistry and thermodynamics of precipitating copper, nickel, cobalt, and cadmium metals by reaction with hydrogen are discussed. Mechanisms of metal precipitation, nucleation, growth, and agglomeration are reviewed, as well as some solubility phenomena of gases and solids at elevated temperatures. Experimental data presented deal mainly with the reaction of copper sulfate solution with Hz.

May 1, 1956

By C. Lottering

Copper sulphate solutions are produced during the pressure leaching of first-stage leach residue in a typical base metal refinery process. Apart from impurities such as selenium and tellurium, this leach solution also contains other precious metals (Rh, Ru, and it) due to dissolution in the pressure leaching stage. Selenium and tellurium are removed from the leach solution by precipitation with sulphurous acid, since these elements negatively affect electrowinning. This study investigates the feasibility of modifying the Se/Te precipitation process step to achieve significant rhodium precipitation in addition to selenium and tellurium precipitation, in order to reduce the rhodium inventory of the process. Thiourea, S02, formaldehyde, formic acid, and sodium thiosulphate were evaluated to determine which of these reagents would achieve the highest Rh precipitation. Based on these screening tests, SO2 and thiourea were selected to be used as precipitation reagents in optimization tests. During these optimization tests, the operating temperature (80 to 150°C) and the amount of reagent added (80 to 140 per cent excess) were varied to evaluate the effects that these operating conditions have on the precipitation behaviour of Rh as well as Se, Te, Cu, and Ni, and to propose appropriate operating conditions. It was found that thiourea resulted in good Rh and Se precipitation (typically in excess of 90 per cent), but precipitated noticeably more copper and nickel from the solution than when SO2 was used. In addition, thiourea had poor Te removal characteristics. SO2 achieved a maximum of 70 per cent precipitation of the rhodium. Faster kinetics and a larger extent of Te precipitation were, however, observed when using SO2 compared to thiourea.

Jan 1, 2012

By N. Geoffroy, E. Benguerel, G. P. Demopoulos

In the late 1990s, a chemical process to remove mercury and selenium from weak sulphuric acid solutions was patented and implemented in the CEZinc refinery in Valleyfield, Quebec. The CEZinc process comprises two stages. In the first one, sodium sulphide is added to the weak acid solution in order to precipitate the soluble mercury. The solution is then treated with sodium dithionite in order to reduce the selenium to elemental form. Because of recent changes in the composition of the industrial solution, a project to study the background chemical reactions was started. In this paper, a review of the background chemistry is presented on the basis of several eh-pH diagrams on one hand, while on the other experimental results are reported dealing with the reaction of selenium (IV) species with either dithionite, sulphide or a combination of the two. According to this work, elemental selenium enjoys a wide pH-eh range stability with selenium sulphide being metastable. Selenium (IV) in single metal synthetic solutions was found to be reduced - to elemental state - at ambient temperature down to ppb range with dithionite as long as the stoichiometric ratio (dithionite/selenium) was in excess of two and the pH < 1.7. Under these conditions the reaction was very fast reaching completion within one minute. Sodium sulphide proved equally effective in reducing selenium (this time as selenium sulphide) to ppb range from single metal solutions. However, in mixed Se-Hg solutions deviations from this "ideal" behaviour was observed resulting in higher levels of residual soluble selenium left in solution.

Jan 1, 2008

By J. A. du Plessis, C. Dorfling

Selenium, tellurium and other precious metals (OPMs, namely Rh, Ru and Ir) dissolve in the final leaching stage of base metal refineries. Se and Te are typically removed from the copper sulphate leach solution by precipitation with sulphurous acid. Recovery of dissolved OPMs is desirable because it will reduce OPM inventory and losses. Thiourea is an effective OPM precipitation reagent, but yields insufficient Te removal. Copper is known to enhance Te precipitation when using sulphurous acid as precipitation reagent. The primary objective of this project was to evaluate whether simultaneous precipitation of Se, Te and OPMs using thiourea with metallic copper as precipitation reagents is possible. Batch precipitation tests were performed to evaluate the effect of temperature (50 – 70°C), thiourea addition (160 – 430% excess) and copper addition (2 – 8 g/L) on Se, Te and OPM precipitation. Increasing the temperature from 50°C to 70°C resulted in an average increase of 55.6 percentage points for Se precipitation and 13.5 – 23.5 percentage points for OPM precipitation. The copper addition did not have a significant impact on the precipitation behaviour. Increasing the thiourea addition increased the precipitation of Se and Te, especially when the copper addition was low; Rh and Ru precipitation also increased with up to 10 and 12 percentage points, respectively. Despite these observations, the precipitation of Se was significantly faster when no thiourea was added. It is not currently clear why thiourea appears to inhibit the Se precipitation by reaction with metallic copper. In general, Te precipitation was low (less than 30%) at the conditions investigated. Simultaneous precipitation of Se, Te and OPMs at temperatures below 80°C does not appear to be a viable option; a multiple stage operation for sequential removal of Se and Te with copper followed by OPM precipitation with thiourea would be required.

Jan 1, 2016

By Jae-Chun Lee

Di-2-ethylhexyl phosphoric acid (D2EHPA) is widely used for separating rare-earth elements. In commercial plants, rare-earths are usually stripped from loaded extractant streams using mineral acid, then precipitated as oxalates. Many rare-earth uses demand specific powder characteristics, which are obtained by secondary processing. This paper demonstrates the feasibility of combining the stripping, precipitation and powder processing stages, thereby achieving considerable savings. MEHPA solutions were loaded with yttrium, then emulsified with oxalic acid-HC1 solutions to precipitate yttrium oxalate, which was readily calcined to yttrium oxide. The precipitation kinetics and yield were sensitive to process conditions. The morphology and size of the yttrium oxalate powders varied with the concentrations of D2EHPA and oxalic acid, and the presence of SPAN 60, which affected nucleation, growth, and the emulsion characteristics.

Jan 1, 1992

By María Cristina Ruiz

Hematite precipitation is a convenient alternative for the removal of iron from leaching circuits because of its chemical stability, high density and high iron content. The precipitation of hematite from ferrous sulfate solutions was studied in a batch reactor. The precipitation occurs by two sequential steps: oxidation of the ferrous to ferric ions followed by hydrolysis of the ferric to hematite. The main objective of this study was to determine the effect of the main operating variables on the rate of two steps of hematite precipitation. The variables studied included: stirring speed (100 to 600 rpm), temperature (160 to 200 ºC), concentration of sulfuric acid (1 to 10 g/L), initial iron concentration (1 to 15 g/L), and partial pressure of oxygen (1 to 6 atm). The sulfur content and the particle size of the solids that precipitated under various conditions were also determined. The results showed that at low temperature and high acid concentration the rate of Fe3+ hydrolysis is the step that controls the overall process. The variable that affects most the rate of Fe2+ to Fe3+ oxidation and the rate of hematite precipitation is the temperature.

Jan 1, 2008

By Taiping Lou

The effects of slag composition, additive agents, and heat treatment conditions on the perovskite (CaO ? TiO2) crystal morphology, the precipitation behavior, the crystal growth and the volume fraction (VF) in the Ti-bearing blast furnace slags were investigated. The morphology of perovskite is dispersed dendriform in molten slags. The crystal growth mechanism of the remelting of fine dendrites and the coarsening of larger grains exists throughout the solidification of molten slags. With the temperature decrease, the VF was increased and Perovskite transformed from fine dendrites to coarsening ones or equiaxed grains. The lower cooling rate can increase the VF and coarsen the grain obviously, while higher cooling rate will decrease the VF and reduce the average equivalent diameter (AED) of Perovskite. When .increasing the content of CaO and Fe20}, the VF can increase obviosly. However, high basicity will give rise to the increasing of viscosity of slag, which result in the reducing of the AED. The experimental results showed that additive CaF2 and MnO can efficiently decreased the viscosity of the slags, and obviously improved the morphology of perovskite and promote growth.

Jan 1, 2000

By Y. Fukunaka, M. Niinae, E. Kusaka, T. Kuzuya, R. Ishii

"Samarium oxalattr particles was precipitated in oxalic acid aqueous solution from samarium-loaded D2EHPA solution emulsified with a conventional impeller. The calculated fractional precipitation of samarium oxalate was reasonably compared with the value determined by chemical analysis. Morphological variation of oxalate precipitate particles was then examined with H2C2O4 concentration in aqueous solution, Sm(III) and D2EHPA concentrations in organic phase. The needle-like precipitate was identified as Sm2(C2O4)3 10H2O by XRD. Precipitates obtained at higher H2C2O4· or Sm(III) concentration greatly decreased the length of major axis of precipitate, while those at higher D2EHPA concentration increased it. The oxalate was further precipitated under ultrasonic irradiation. However, the morphological variation caused by theses processing variables was not so evident under ultrasonic irradiation as in an impeller or shaking mixer.IntroductionThe materials processing of the rare earth elements must be reviewed from the scope of industrial ecology, since they have the potential applications of magnetic materials as well as secondary battery in developing programs of the electric vehicle. The technological trend to develop the electric vehicle may greatly influence the concept of materials processing, since the global· environmental problem must accommodate with the sustainable development for mankind. The recycle design must be a key issue in the materials science and engineering.Solvent extraction provides a unique separation technology -in this sense. Doyle (1)(2) reported the integrating solvent extraction with processing of advanced ceramic materials, whose chemical composition and microstructure must be precisely controlled. In her paper, the higher productivity inherent to the present process superior to hydrolyzing metal alkoxides was emphasized. Oxalic acid has been used as precipitant for rare earth purification process, since rare earth oxalate has a very small solubility in water and can be easily decomposed to oxide. It is thus suitable for precipitation stripping agent in cationic exchange type extracting system (i.e. D2EHPA, VA-10, PC-88A and so on)."

Jan 1, 2000

By R. H. Harrington

THE definition of precipitation-hardening is well understood and its principles have been subjected to study for some time. However, the variation of properties with double aging, combined with strain-hardening, gives promise of new and useful phenomena. Properly to understand these distinctions, definitions of these terms are necessary. Precipitation-hardening. This reaction usually depends upon an alloy having such a composition that it consists only, or in major part, of but one phase, a solid solution, at a high temperature, so that, upon slow cooling, this solution breaks down into two phases, the solid solution and a compound. By heating the alloy to the temperature for maximum solution of the compound, quenching, and reheating to a suitable lower temperature for critical dispersion precipitation of the compound, useful properties of the alloy may be developed to a maximum. Double Aging.-Dougle aging in part is similar to the process for precipitation-hardening, consisting of heating a precipitation-hardening alloy to the solution temperature, quenching, reheating to the suitable dispersion precipitation temperature, strain-hardening, and again reheat-ing to a suitable temperature to develop certain useful properties to a maximum. The strain-hardening may be induced by two methods: (1) a rate of cooling from the first reheat may suffice to strain the solid solution lattice of the alloy; or (2) the alloy may be cold-worked to a suitable degree between the two reheats.

Jan 1, 1936

By J. W. Halley

COPPER has frequently been recommended as an alloying element for steel and the precipitation-hardening of steels containing from 1 to 2 per cent copper has been studied by a number of investigators. The straight copper steels, however, have not been used extensively and little advantage has been taken of the precipitation-hardening of complex steels containing appreciable amounts of copper. It is diffi-cult to produce a satisfactory surface on the straight copper steels and undoubtedly this has discouraged their use. During recent years a number of steels containing enough copper to make them susceptible to precipitation-hardening have been put on the market. These steels belong to the group usually referred to as "low-alloy high-tensile" steels. They were designed for use in the "hot-rolled" condition; transportation equipment and large structures that cannot be readily heat-treated have been their chief application. Little emphasis has been placed on the possibility of strengthening those containing substantial amounts of copper by precipitation-hardening. The present investigation was undertaken to determine the precipitation-hardening characteristic of one of the "low-alloy steels."

Jan 1, 1940

By Vernon Read

Among the technical problems in AEC&apos;s Project Plowshare is the necessity of determining the precise effects of nuclear blasts in all kinds of ground formations. This calls for extensive in-situ sampling with full core recovery. In the exploration drilling that often precedes a new test detonation, the AEC and its contractors have applied both novel and established sampling techniques in many new ways, giving improved core recovery and reduced costs in all subsurface sampling and testing. Unique among these new techniques is one that achieved full recovery and virtually undisturbed samples from near-surface layers of unconsolidated boulder-strewn alluvium. This approach involves a combination of oilfield and mining core drilling equipment. Oilfield heavy drill collars, rotary stabilizers and thick, vibration-reducing oil emulsion drilling mud were used in combination with the precise hydraulic feed control, fast (over 300 rpm) bit rotation, light drilling weight, hard rock core barrels and multi-step diamond bits that are common in mining industry diamond drilling.

Jan 8, 1963