Dynamic modeling and optimal control of goethite process based on the rate-controlling step

The iron removal process is an important technology in zinc hydrometallurgy. Due to its complicated reaction mechanism, it is difficult to highly control the performance of process solely relying on manual experience. Therefore, this paper focuses on the dynamic modeling for the goethite process and its optimal control method. In different reactors, different operating conditions will influence the rate-controlling step of process reactions, as well as the kinetic model. We determine the rate-controlling step of reactions in each reactor according to the reaction conditions, and subsequently the dynamic model has been developed based on the rate-controlling step. Then an optimal control method for the goethite process has been proposed, which satisfies the technical requirements with minimal process consumption. The proposed optimal control includes pre-setting of descent gradient of outlet ferrous ion concentration and optimal control of oxygen and zinc oxide. The simulation results demonstrate that the proposed dynamic model exhibits greater performance comparing with the process model without considering rate-controlling step, and the proposed control strategy has a higher satisfactory than the nonlinear model predictive control. Then, the proposed optimal control is validated by the industrial experiment, which the average oxygen and zinc oxide consumptions decreased by 568 m³/day (6.22%) and 3.09 t/day (5.16%) and the qualified rate of outlet ferrous ion concentrations increased by 5.5%, compared with the manual control.     

Dissolution kinetics of dehydroxylated nickeliferous goethite from limonitic lateritic nickel ore

The dissolution kinetics in 2 M H₂SO₄ of variously dehydroxylated nickeliferous goethites was investigated for five oxide-type lateritic nickel deposits. Goethite was the main constituent with minor amounts of quartz, talc, kaolinite and Mn oxides. Dissolution of Fe from heated materials followed the Kabai equation. There was a 9–34-fold increase in the Kabai dissolution rate constant (k) for samples heated at 340–400 °C due to both the increased surface area (1.5–2.6 fold) and higher density of structural defects (5–10 fold) in the variously dehydroxylated products. The presence of structural Al and Cr in goethite appears to reduce dissolution rate possibly through the greater M³⁺–OH, O bond strength relative to Fe³⁺, Ni²⁺–OH, O. Nickel showed congruent dissolution with Fe indicating that Ni was uniformly incorporated in the goethite structure. Pre-heating goethite to 600–800 °C for 30 min resulted in incongruent dissolution of Fe and Ni. It is postulated that some Ni is ejected from the neo-formed hematite structure and resides on the crystal surface or in voids. These results may contribute to the development of more efficient procedures for Ni extraction including heap leaching of lateritic nickel ores.     

Comparative leaching of minerals by sulphuric acid in a Chinese ferruginous nickel laterite ore

The Yuanjiang nickel laterite ore containing mainly maghemite, goethite and lizardite was leached by sulphuric acid at atmospheric pressure and the residues were characterized using X-ray diffraction and scanning electron microscopy/X-ray energy dispersive spectroscopy. The relationship was discussed between the extraction of nickel, cobalt, iron, magnesium, aluminum, and the dissolution behaviour of the laterite minerals; as well as the extent of congruency of nickel, cobalt and iron extraction. The results show that the solubility of the laterite minerals in sulphuric acid decreases in the following order: lizardite > goethite > maghemite > magnetite ≈ hematite > chromite ≈ ringwoodite. Lizardite dissolved rapidly in 0.6 mol/L sulphuric acid at 60 °C whilst goethite dissolved completely in 2.5 mol/L sulphuric acid at 80 °C. The dissolution of the primary mineral maghemite was slow, but increased with increasing acid concentration and leaching temperature. Magnetite dissolved more slowly than maghemite; and hematite was only dissolved in > 6.2 mol/L sulphuric acid at 105 °C. Chromite and ringwoodite were not dissolved. The leaching behaviour of the laterite minerals may be explained by the bond strength differences of Me–O and the substitution of metal cations in the mineral structure.     

Turning Industrial Residues into Resources: An Environmental Impact Assessment of Goethite Valorization

Goethite is a metals-rich residue that occurs during zinc production. The feasibility of metal recovery from goethite has been demonstrated, but is not economically viable on an industrial scale. Therefore, goethite is landfilled with considerable economic costs and environmental risks. The goal of this study is to evaluate the environmental performance of a new valorization strategy for goethite residues from zinc production, with the aims of: ① recovering the valuable zinc contained in the goethite and ② avoiding the landfilling of goethite by producing a clean byproduct. The presented goethite valorization strategy consists of a sequence of two processes: ① plasma fuming and ② inorganic polymerization of the fumed slag. Plasma fuming recovers the valuable metals by fuming the goethite. The metals-free fumed slag undergoes a process of inorganic polymerization to form inorganic polymers, that can be used as a novel building material, as an alternative to ordinary Portland cement (OPC)-based concrete. Life-cycle assessment (LCA) is used to compare the environmental performance of the inorganic polymer with the environmental performances of equivalent OPC-based concrete. The LCA results show the tradeoff between the environmental burdens of the fuming process and inorganic polymerization versus the environmental benefits of metal recovery, OPC concrete substitution, and the avoidance of goethite landfilling. The goethite-based inorganic polymers production shows better performances in several environmental impact categories, thanks to the avoided landfilling of goethite. However, in other environmental impact categories, such as global warming, the goethite valorization is strongly affected by the high-energy requirements of the plasma-fuming process, which represent the environmental hotspots of the proposed goethite recycling scheme. The key elements toward the sustainability of goethite valorization have been identified, and include the use of a clean electric mix, more effective control of the fumed gas emissions, and a reduced use of fumed slag through increased efficiency of the inorganic polymerization process.     

Photodegradation of phenol red in the presence of oxyhydroxide of Fe(III) (Goethite) under artificial and a natural light

The (α‐FeOOH) Goethite composite is a stable and an efficient catalyst in aqueous suspension under irradiation at 365 nm and by solar light. The photocatalytic activities of this composite were evaluated using Phenol Red (PR) dye (phenolsulfonphthalein class). In the dark, controlling factors, such as the pH and the adsorption of PR on Goethite surface were evaluated (before starting the photochemical experiments). It was found that the system PR‐Goethite present a small decrease in the main band of the dye (435 nm) which was explained by the low rate of adsorption of this dye on the Goethite. Also, we note that 40% of PR decolourisation was obtained after 200 min by the system PR‐Goethite‐hydrogen peroxide (H₂O₂) in dark due to the formation of ^?OH by thermal decomposition of H₂O₂ on the surface of Goethite. The effects of various experimental parameters, such as initial dye concentration, pH, photocatalyst amount, tert‐Butyl alcohol effect and H₂O₂ addition were investigated in the study of photodegradation of the dye. The results showed that the photodegradation of PR under UV‐A (365 nm) irradiation could be enhanced greatly in the presence of H₂O₂. Natural radiation tests (under sunlight) showed that degradation was faster comparing with that obtained using the artificial one at 365 nm. Studies of the mineralization using total organic carbon method under naturel light certify that this method, compatible with the environment, may be considered in the treatment of wastewater and generally in the process of removal of this kind of pollutant.     

Pressure acid leaching of arid-region nickel laterite ore: Part I: effect of water quality

The effect of water salinity on the reactions occurring during pressure acid leaching of an arid-region laterite ore, using hypersaline water, seawater, sub-potable water and tap water, is examined. Particular emphasis is placed on the mineralogy of the residue and its implications with regard to residue volume/mass, overall acid consumption and nickel extraction. Analysis of a pressure acid leach residue by electron microprobe indicates that the residual nickel is present in phases that contain silicon and varying concentrations of aluminium, but are deficient in sulphur. Incomplete extraction of nickel from the ore may not be attributed to any one mineral phase.     

Adsorption of uranyl ions and microscale distribution on Fe-bearing mica

The interaction of uranyl ions (UO₂²⁺) with Fe-bearing mica is an important determinant of the mobility of U species in granitic rocks or their weathered terrains, especially with regard to radionuclide migration. To understand their interaction, U sorption experiments were conducted on both fresh and oxidized biotites, especially examining an effect of oxidized mineral surfaces which was treated by H₂O₂ for 3 weeks. The U sorption onto the biotite reached a maximum at around pH 7.0, and the amount adsorbed by the oxidized biotite was much larger than that by the fresh one. The difference of the adsorption capacity between the two biotites may be attributed to an increase in the specific surface area by oxidization, which accompanies some slightly peeled off and reactive surfaces with amorphous precipitates. During the U adsorption reaction, there was a continuous depletion of K⁺ ions from the interlayer space. At the same time structural Fe was released and oxidized near the edges, forming non-detectable very small goethite particles. Such an incipient feeble crystalline Fe (hydr)oxide phase was only detected by scanning electron microscopy (SEM), but its location interestingly corresponded to the U adsorbed position on the biotite surface, implying its strong adsorption of U. Besides, the crystallized Fe (hydr)oxide seems to be relatively more effective in the adsorption of U as compared with the amorphous one on the H₂O₂ treated biotite.     

Enhancing mineral liberation of a Canadian rare earth ore with microwave pretreatment

Liberation, as an attribute of mineralogy characteristic, whose impacts on finely disseminated Canadian rare earth ore was studied with microwave pretreatment. Samples of a light rare earth ore along with mostly ankerite and biotite as dominant gangue minerals as well as bastnaesite, strontianite and goethite as dominated minerals were exposed to further comminution by ball mill and microwave pretreatment fragmentation. Mineralogical characteristics were analyzed by using a mineral liberation analyzer (MLA). The results indicated that tight association mutually penetrates among dominated minerals in the range size of ?300 + 212 μm and ?212 + 150 μm and gangue minerals in the form of adjacent type, fine vein type, shell type and packing type. Temperature in the ore samples pre-treated by microwave can rapidly rise to 250 °C with microwave power of 0–1.5 kW and microwave time of 0–2 min. Applying the microwave pretreatment merely reduces the hardness of the ore causing the fracture of rare earth ore, but this does not transform or change the original mineralogy characteristics of the ore samples. On the basis of above study, the liberation value of bastnaesite, strontianite and goethite with microwave pretreatment is greater than with conventional comminution when the liberation class is above 75%. The distribution of particle size of rare earth ore samples is better with microwave pretreatment than with conventional comminution for particle size of 7.4 × 10^?5 m. With microwave pretreatment, the theoretical grade–recovery of bastnaesite, strontianite and goethite in the rare earth ore attains better results than with conventional comminution at a given grade.     

用针铁矿法从锌焙烧烟尘的热酸浸出液中除铁

研究了从锌焙烧烟尘常压热酸浸出液中沉淀针铁矿的过程。试验结果表明,反应时间和空气流量对除铁率的影响不显著,而反应温度和溶液终点pH是除铁过程的主要影响因素。在终点pH3.0、反应温度333 K、反应时间2 h、空气流量0.2 m3/min的条件下,除铁率超过99.5%,溶液中铁浓度可由40g/L降至0.1 g/L以下。     

Study on kinetics of thermal decomposition of low LOI goethetic hematite iron ore

In the present study, the kinetics of thermal decomposition of hydrated minerals associated in natural hematite iron ores has been investigated in a fixed bed system using isothermal methods of kinetic analysis. Hydrated minerals in these hematite iron ores are kaolinite, gibbsite and goethite, which contribute to the loss on ignition(LOI) during thermal decomposition. Experiments in fixed bed have been carried out at variable bed depth(16, 32, 48 and 64 mm),temperature(400-1200 ℃) and residence time(30,45, 60 and 75 min) for iron ore samples. It is observed that beyond a certain critical bed depth(16 mm), 100% removal of LOI is not found possible even at higher temperature and higher residence time. Most of the solid-state reactions of isothermal kinetic analysis have been used to analyze the reaction mechanism. The raw data are modified to yield fraction reacted "α" versus time and used for developing various forms of "α" functions.f(α) is the inverse of first derivative of g(α) with respect to α. The study demonstrates that decomposition of hydrated mineral in hematite follows the chemical kinetics.The estimated activation energy values in all the experimental situations are found to high, of the order of 60 kJ/mol, reinstating that the reactions are indeed controlled by moving phase boundary and random nucleation.