Process for the Recovery of Cobalt and Nickel from Sulphate Leach Liquors with Saponified Cyanex 272 and D2EHPA

Abstract

In this paper, a process is reported for the recovery of cobalt and nickel from copper raffinate solutions using partially saponified Cyanex 272 and D2EHPA as the extractants. The aqueous feed contains 1.65 g/L cobalt and 16.42 g/L nickel. More than 99.9% cobalt separation was achieved with 0.13 M Cyanex 272 (60% neutralized with alkali) in two counter‐current stages at an aqueous to organic phase ratio of 1.1:1. Co‐extraction of nickel was 0.18% only. Stripping of cobalt from a loaded organic phase was carried out with synthetic spent electrolyte solution at an organic to aqueous phase ratio of 2.5 in two counter‐current stages to generate a pregnant electrolyte solution to produce cobalt metal by electrowinning. Similarly, optimum conditions for nickel extraction with 60% neutralized 1 M D2EHPA at O/A ratio of 1.4 in 2 two stages and stripping of metal with synthetic spent electrolyte at O/A ratio of 1.6 in two stages were standardized. Extraction and stripping efficiencies were >99% and the flowsheet of the process is demonstrated.     

Simultaneous Recovery of Nickel and Cobalt from Aqueous Solutions using Complexation-Ultrafiltration Process

Simultaneous recovery of nickel and cobalt from aqueous solutions by complexation-ultrafiltration process with polyethylenimine (PEI) was studied. Experiments were performed as a function of polymer/metal ratio (P/M), solution pH, and ionic strength. Effects of concentration time on metal rejection and membrane flux were also studied. At optimum experimental conditions of pH 6.0 and P/M 5.0, the nickel removal efficiency reaches at 99.9% and cobalt removal efficiency goes to 96.4%. Both nickel and cobalt removal efficiencies decreased as the adding salt concentration increases. During 12 h of the ultrafiltration process, the decline of membrane flux was less than 16% and the removal efficiencies for both nickel and cobalt were kept almost constant. Diafiltration was further performed to regenerate PEI. The removal efficiencies for both metals using recycled PEI were found to be close to those with the original PEI. Results from the two-step process of complexation-UF and decomplexation-UF separation showed that it could be a promising method for simultaneous recovery of nickel and cobalt from aqueous solutions.     

Biodiesel production from waste cooking oil via alkali catalyst and its engine test

Waste cooking oils (WCO), which contain large amounts of free fatty acids produced in restaurants, are collected by the environmental protection agency in the main cities of China and should be disposed in a suitable way. Biodiesel production from WCO was studied in this paper through experimental investigation of reaction conditions such as methanol/oil molar ratio, alkaline catalyst amount, reaction time and reaction temperature which are deemed to have main impact on reaction conversion efficiency. Experiments have been performed to determine the optimum conditions for this transesterification process by orthogonal analysis of parameters in a four-factor and three-level test. The optimum experimental conditions, which were obtained from the orthogonal test, were methanol/oil molar ratio 9:1, with 1.0 wt.% sodium hydroxide, temperature of 50 °C and 90 min. Verified experiments showed methanol/oil molar ratio 6:1 was more suitable in the process, and under that condition WCO conversion efficiency led to 89.8% and the physical and chemical properties of biodiesel sample satisfied the requirement of relevant international standards. After the analysis main characteristics of biodiese sample, the impact of biodiesel/diesel blend fuels on an YC6M220G turbo-charge diesel engine exhaust emissions was evaluated compared with 0# diesel. The testing results show without any modification to diesel engine, under all conditions dynamical performance kept normal, and the B20, B50 blend fuels (include 20%, 50% crude biodiesel respectively) led to unsatisfactory emissions whilst the B′20 blend fuel (include 20% refined biodiesel) reduced significantly particles, HC and CO etc. emissions. For example CO, HC and particles were reduced by 18.6%, 26.7% and 20.58%, respectively.     

Determination of the Optimum Conditions for Copper Leaching from Chalcopyrite Concentrate Ore Using Taguchi Method

The optimum conditions for the extraction of copper from chalcopyrite concentrate into SO₂-saturated water were evaluated using the Taguchi optimization method. High level copper recovery was obtained in an environmentally friendly process that avoids sulfur dioxide emission into the atmosphere because SO₂ forming in the roasting is used in the dissolution. Experimental parameters and their ranges were chosen as follows: reaction temperature, 293–333 K; solid-to-liquid ratio, 0.025–0.15 g/mL; roasting time, 30–90 min; roasting temperature, 773–973 K; stirring speed, 400–800 rpm; and reaction time, 10–60 min. The particle size and gas flow rate were 63 µm and 10 cm³/min, respectively. The optimum conditions of the dissolution process were determined to be reaction temperature of 318 K, a solid-to-liquid ratio of 0.025 g mL^?1, a roasting time of 75 min, a roasting temperature of 773 K, a stirring speed of 400 rpm, and a reaction time of 30 min. Under optimum conditions, dissolution yield of copper was 91%.     

Aqueous Two-Phase Extraction of Lactic Acid: Optimization by Response Surface Methodology

In this study a suitable alcohol/salt aqueous two-phase (ATP) system was selected for the recovery of lactic acid from an aqueous solution. From the different ATP systems studied, the ethanol/dipotassium hydrogen phosphate ATP system appeared to be favorable. To examine the potential of this ATP system, the extraction yield of lactic acid in aqueous solutions was optimized with the response surface methodology. The parameters studied were concentrations of ethanol (22.00–38.80%, w/w), dipotassium hydrogen phosphate (15.00–31.80%, w/w) and lactic acid (26.36–93.64 g/L). The optimum conditions were found to be 30.23% w/w ethanol, 18.40% w/w dipotassium hydrogen phosphate, and 80 g/L lactic acid. Under these conditions, a favorable extraction yield of lactic acid was obtained. The maximum partition coefficient of lactic acid and extraction yield was determined as 2.26 and 87%, respectively. The optimum extraction conditions were then used to guide the recovery of lactic acid from a real fermentation broth. As a result, the partition coefficient and extraction yield of lactic acid reached 2.06–80%, respectively.     

Typoselectivity of Crude Geobacillus sp. T1 Lipase Fused with a Cellulose-Binding Domain and Its Use in the Synthesis of Structured Lipids

Typoselectivity of crude CBD-T1 lipase (Geobacillus sp. T1 lipase fused with a cellulose binding domain) was investigated. Multi-competitive reaction mixtures including a set of n-chain fatty acids (C8:0, C10:0, C12:0, C14:0, C18:1 n-9, C18:2 n-6 and C18:3 n-3) and tripalmitin-enriched triacylglycerols were studied in hexane. The crude CBD-T1 lipase discriminated strongly against C18:1 n-9 [competitive factor (α) = 0.23] and showed the highest preference for C8:0 (α = 1). Utilizing the catalytic properties of crude CBD-T1 lipase, acidolysis of soybean oil with C8:0 was selected as a model reaction to investigate the ability of the lipase to produce MLM-type (medium-long-medium) structured lipids. Several reaction parameters (added water amount, reaction temperature, substrate molar ratio and reaction time) examined for incorporating C8:0 into soybean oil, the optimum conditions were: 1:3 (soybean oil/C8:0) of molar ratio, 3 mL of hexane, 50 °C of temperature, 48 h of reaction time, 20 % of crude CBD-T1 lipase (w/w total substrates), and 7.5 % of water (w/w enzyme). Under these conditions, the incorporation of C8:0 was 29.6 mol%. The results suggest that crude CBD-T1 lipase, which showed different fatty acid specificity profiles, is a potential biocatalyst for the modification of fats and oils.     

Efficient Cycle Recovery of Hydrogen from a Low Concentration Pyrolysis Gas Stream by Pressure Swing Adsorption – An Experimental Evaluation

Breakthrough curves, cycle mass balances, and cycle bed productivities (mg H₂ per gram of adsorbent) on three dual adsorbent amounts (g) of 2,892, 1,963, and 1,013 respectively each filling 200 cm, 135 cm, and 70 cm of a 5.0 cm internal diameter stainless steel pipe were performed. The approximate optimum (sludge pyrolysis) synthesis gas with composition in volume % of 45% H₂/35% CO/20% CH₄ was used as the feed gas with molecular sieve 5 Å and activated carbon as adsorbents. Impurity breakthroughs occurred at ～14.9, 12.3, and 5.0 minutes respectively for % cycle recoveries of 72.2, 65.0, and 60.2 using 2,892, 1,962, and 1,013 g of adsorbent respectively. Our results indicated that basing % recycle recovery on cycle bed productivity can enable efficient hydrogen recovery with savings on adsorbent amount. An optimum cycle bed productivity of 2.3 mg H₂/g of adsorbent corresponded to a cycle recovery of 66.2% for 2,300 g of adsorbent used. Only 1.7 mg H₂/g of adsorbent was obtained for a cycle recovery of 72.2% requiring up to 2,800 g of adsorbent. This makes economic sense in the pressure swing adsorption separation of hydrogen from traditionally low hydrogen concentration biomass sources.     

Influence of pre-soaking conditions on ultrasonic extraction of Spirulina platensis proteins and its recovery using aqueous biphasic system

Ultrasonic aqueous extraction of proteins from dry Spirulina platensis at acidic (ACSU), alkali (ALSU), and neutral (NSU) conditions and its recovery using aqueous biphasic system (ABS) was studied. S. platensis was soaked in the solvent for 12 h prior to extraction. Neutral condition showed a higher protein release of 18.6 mg/ml at optimum conditions (solid–liquid ratio 1:20, 80% ultrasound amplitude, 100% ultrasound duty cycle, and 4ºC). The Box–Behnken design (BBD) suggested optimum conditions for ABS (PEG 6000, pH 8, and 5% NaCl) and gave 84.1% recovery. Although microscopic observations indicated structural changes, sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) and Fourier-transform infrared spectroscopy (FTIR) analyses confirmed that the proteins are intact.     

Chemical conversion of PET waste using ethanolamine to bis(2-hydroxyethyl) terephthalamide (BHETA) through aminolysis and a novel plasticizer for PVC

Poly(ethylene terephthalate) (PET) recycling has been carried out by various methods, e.g., mechanical recycling, chemical recycling and energy recovery method. In this study, chemical recycling of PET was carried out by aminolysis using ethanolamine and converted into bis(2-hydroxyethyl) terephthalamide (BHETA). The reaction was performed by varying the PET:ethanolamine ratio, reaction time and catalyst used for waste medical grade bottles of PET. Yield of about 81 % was obtained for PET:ethanolamine ratio of 1:4 (w/w), with 3 h reaction time, at 160 °C with zinc acetate as a catalyst. BHETA was characterized with FTIR, ¹H NMR, and DSC analysis. BHETA was further reacted with heptanoic acid at a molar ratio of 1:2.5. The product obtained was used as a plasticizer for PVC at 5, 10, 15 and 20 parts per hundred (phr) concentration. Thermal and mechanical tests were carried out and the result obtained was compared with the virgin PVC without plasticizer and with conventional plasticizer of PVC, i.e., dioctyl phthalate at 15 phr concentration since new plasticizer showed excellent properties at 15 phr concentration. This newly synthesized plasticizer was completely fused with PVC and in tensile testing helped in increasing the elongation, which was an indication of the plasticization effect shown by this developed material. Glass transition temperature also decreased with an incorporation of the new plasticizer as compared to virgin PVC.     

Supercritical Carbon Dioxide Extraction of Marigold Lutein Fatty Acid Esters: Effects of Cosolvents and Saponification Conditions

Extraction of lutein fatty acid esters from marigold flower using supercritical carbon dioxide (SC-CO₂) with cosolvent was investigated. Without the cosolvent, the total xanthophylls yield increased with increasing temperature and pressure of SC-CO₂, and the optimal condition was found to be at 60°C and 40 MPa. At this condition, the highest total xanthophylls percent recovery was 74.4 ± 0.9%. Palm oil was found to be a more efficient cosolvent than soybean oil, olive oil, and ethanol, resulting in a 16% increase in the total xanthophylls recovery to 87.2 ± 4.4% when 10% (w/w) of palm oil was used. Furthermore, saponification of the oleoresin for 3 h at 75°C with 40% w/v KOH solution at the oleoresin to solution ratio of 1 g to 2 ml was found to suitably convert lutein fatty acid esters into free lutein.     

Synthesis and characterization of a novel high‐oil‐absorbing resin

A high‐oil‐absorbing resin, which was a low crosslinking resin, was synthesized by conventional suspension copolymerization in this study. The effects of the monomer ratio, crosslinker, initiator, ratio of water to oil, and defined optimum reaction conditions were studied. The highest oil absorptivity of the resin was about 11.5 g/g in diesel and the oil‐absorption saturation time was 3 days when the best process conditions were as follows: ratio of styrene to ethylene–propylene–diene terpolymer = 40/60 w/w, amount of crosslinker divinylbenzene = 1.0 wt %, amount of benzoyl peroxide = 1.0 wt %; proportion of gelatin to calcium phosphate = 0.2 g/0.1 g, stirring speed = 500 r/min, and proportion of water to oil = 15 : 1. By using such methods as infrared spectroscopy, thermogravimetric analysis, and other methods, we studied the oil‐absorbing resin structure, oil‐absorption rate, oil‐absorption saturation time, and oil‐absorption rate twice. The oil‐absorbing resins were used repeatedly through the extraction of ethanol. The experiment results show little effect on the oil‐absorption properties. The oil‐absorption rate constant was evaluated for diesel, and the oil‐absorbing process obeyed the first‐order kinetics equation. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Liquefaction of Red Pine Wood,Pinus densiflora,Biomass Using Peg-400-Blended Crude Glycerol for Biopolyol and Biopolyurethane Production

Red pine wood, Pinus densiflora, biomass was liquefied through liquefaction using a solvent mixture of crude glycerol and PEG-400 with a sulfuric acid catalyst. The liquefaction process parameters of crude glycerol/PEG-400 blending ratio, biomass loading, acid loading, reaction temperature, and reaction time were optimized. Biopolyol with 61.9% biomass conversion was produced at 170°C within 1 h using a co-solvent of crude glycerol and PEG-400 (5/5, w/w), 15% biomass loading, and 3% sulfuric acid loading. The biopolyol possessed a 4.2 mg KOH/g acid number and 892.4 mg KOH/g hydroxyl number. Polyurethane foam was successfully synthesized from the liquefied red pine wood biomass with toluene diisocyanate. The synthesis of biopolyurethane derived from red pine wood biopolyol was confirmed with FT-IR.     

Fractionation of Pre‐Hydrolysis Products from Lignocellulosic Biomass by an Ultrafiltration Ceramic Tubular Membrane

Abstract

Development of the lignocellulosic‐biomass‐based biorefinery for making transportation fuels requires the production of valuable byproducts, minimizing the chemical consumables, and efficient water recovery and reuse. Our focus is on a liquid stream containing a variety of soluble lignin species and alkalinity that is produced by a novel extrusion reactor that was used to break down corn stover to cellulose, sugar acids, and lignin. We report on the ambient temperature fractionation of this byproduct stream with a γ‐alumina ceramic tubular membrane. There are four primary figures‐of‐merit investigated in this study: permeance decline, total organic carbon recovery (TOC) and sodium recovery, and the average molecular mass of organic compounds rejected and permeated. These fractionation results are compared relative to differing feed compositions, recovery, and flux. There was definite fractionation between organic (mostly soluble lignin) compounds. The average molar mass of the organic compounds in the permeate remained around 1000 g/mol; however, they ranged from 1500–4000 g/mol in the retentate. In contrast to the TOC, there was no rejection of sodium ions by the membrane (a desirable objective.) With respect to flux decline, the primary form of resistance (>99%), causing significant permeance decline, was a gel/deposition layer formed on the membrane surface. However, this could be flushed away with periodic rinses using water and/or 0.1 M NaOH. After operation at a cumulative filtration load of ～4.9 Mg/m² with various soluble lignin containing streams, 70% of the membrane's virgin pure water permeance could be recovered by a more vigorous cleaning with 0.1 M NaOH including soaking and permeation. Our results seem very consistent with those previously observed for membrane applications within the pulp and paper industry.     

Study on Streptomycin Sulfate Recovery by Batch Foam Separation

The feasibility of foam separation as a technique was assessed for the recovery of streptomycin sulfate from the waste solution by using an anionic surfactant sodium dodecyl sulfate (SDS). The experimental parameters examined were SDS concentration, superficial gas velocity, initial pH, and liquid loading volume. The results showed that sodium dodecyl sulfate as the surfactant for foam separation had good foaming quality and could effectively concentrate streptomycin sulfate of the aqueous solution by technology of foam separation. The enrichment ratio and the recovery rate of streptomycin sulfate were 4.0 and 85%, respectively under the best operating conditions of sodium dodecyl sulfate concentration 0.4 g/L, superficial gas velocity 300 mL/min, liquid loading volume 300 mL and initial pH 6.0 when streptomycin sulfate concentration was 0.5 g/L.     

Hydrogenation of heptaldehyde to heptyl alcohol with nickel catalysts

Hydrogenation of heptaldehyde to heptyl alcohol was studied with W2 Raney nickel catalyst, prepared in the laboratory, commercial Raney nickel catalyst and Rufert nickel catalyst by varying temperature, catalyst concentration, hydrogen pressure and reaction time. The products were analyzed by gas-liquid chromatography on SE-30 column. The optimum conditions found for quantitative conversion (99.6%) of heptaldehyde to heptyl alcohol were: temperature, 100°C, W2 Raney nickel catalyst concentration, 2% based on heptaldehyde (w/w), hydrogen pressure, 145 psig and reaction time, 1 h. IICT Communication No. 3085.     

Biodiesel production from oleander (<Emphasis Type="Italic">Thevetia Peruviana</Emphasis>) oil and its performance testing on a diesel engine

Oleander oil has been used as raw material for producing biodiesel using ultrasonic irradiation method at the frequency of 20 kHz and horn type reactor 50 watt. A two-step transesterification process was carried out for optimum condition of 0.45 v/v methanol to oil ratio, 1.2% v/v H₂SO₄ catalyst, 45 °C reaction temperature and 15min reaction time, followed by treatment with 0.25 v/v methanol to oil ratio, 0.75% w/v KOH alkaline catalyst, 50 °C reaction temperature and 15 min reaction time. The fuel properties of Oleander biodiesel so obtained confirmed the requirements of both the standards ASTM D6751 and EN 14214 for biodiesel. Further Oleander biodiesel-diesel blends were tested to evaluate the engine performance and emission characteristics. The performance and emission of 20% Oleander biodiesel blend (B20) gave a satisfactory result in diesel engines as the brake thermal efficiency increased 2.06% and CO and UHC emissions decreased 41.4% and 32.3% respectively, compared to mineral diesel. Comparative investigation of performance and emissions characteristics of Oleander biodiesel blends and mineral diesel showed that oleander seed is a potential source of biodiesel and blends up to 20% can be used for realizing better performance from an unmodified diesel engine.     

Recovery of nickel from spent catalyst from palm oil hydrogenation process using acidic solutions

In this study, recovery of nickel from spent catalyst from palm oil hydrogenation process is carried out via extractive leaching process using sulfuric and hydrochloric acids. The effects of acid concentration, solid-liquid ratio, temperature and digestion time on the recovery (acid dissolution) process are investigated. It is found that sulfuric acid is the better leaching solution as compared to hydrochloric acid for recovery (dissolution) of nickel from the spent catalyst. Results from speciation modelling using VMINTEQ further imply that nickel can form sulfate complexes which are more stable than chloride complexes at concentrations higher than 1 M. The optimum conditions for maximum recovery at 85% are achieved at 67% sulfuric acid concentration, digestion time of 140 min, solid-to-liquid ratio of 1:14 and reaction temperature of 80 °C. At solution temperatures higher than 80 °C, the percentage nickel extraction is reduced. The optimization study presented here is useful for spent catalyst generators in the palm oil industry intending to recover valuable metals which may assist in reducing palm oil processing costs.     

Synthesis and characterization of graft copolymer of sodium alginate and poly(itaconic acid) by the redox system

In this study, grafting of itaconic acid (IA) onto sodium alginate (NaAlg) using cerium(IV) ammonium nitrate/nitric acid (CAN/HNO₃) as redox system was carried out by free radical polymerization. The structures of the grafted copolymers (NaAlg-g-PIA) were characterized by ATR-FTIR spectroscopy, NMR spectroscopy, scanning electron microscopy, and thermogravimetric analysis. The reaction conditions for maximum grafting were optimized by varying the reaction time, temperature, percentage of sodium alginate, monomer, initiator, and nitric acid concentrations. The optimum reaction conditions were obtained with reaction time of 5 h, reaction temperature of 30 °C, IA concentration of 0.92 M, CAN concentration of 1.368 × 10^?1 M, HNO₃ concentration of 0.094 M and percentage of NaAlg 0.5 g/dL. The solubility test of NaAlg-g-PIA was also investigated using solvents. The results indicate that prepared graft copolymer was non-soluble in the various solvents, while it was soluble only in saturated solution of NaOH and promising as an adsorbent.     

Optimization of Osmotic Dehydration of Potato Cubes Under Pulsed Microwave Vacuum Environment in Ternary Solution

Optimization of the process parameters for osmotic dehydration of 12.2-mm potato cubes was carried out using response surface methodology. The experiments were conducted using a central composite rotatable design (CCRD) with four factors, viz. sucrose concentration (27.5–42.5% w/w), salt concentration (7.5–12.5% w/w), total osmosis time (26.25–68.75 min), and microwave power density for the initial 4 min (0.375–1.125 W/g of total weight of solution and potato cubes) at two levels each to take into account the individual and interaction effects of the factors. A sample-to-solution ratio of 1:10 and pressure of 0.16 kPa for the initial 4 min were kept constant throughout all of the experiments. It was found that the linear effects of all factors on the water loss (WL) and solids gain (SG) were highly significant. The optimum condition was found at a sucrose concentration of 36.35%, salt concentration of 12.50%, osmosis time of 68.72 min, and microwave power density of 0.38 W/g for the initial 4 min, with a WL of 37.26% initial weight and SG of 8.74% initial weight. The drying of potato cubes was carried out using hot air, microwave–vacuum, and osmotic microwave–vacuum drying methods. It was found that potato cubes dried by combined osmotic microwave–vacuum had better sensory qualities.     

Optimization of an Aqueous Extraction Process for Pomegranate Seed Oil

Response surface methodology employing a five-level, four-variable central composite rotatable design was applied to study the effects of extraction time, extraction temperature, pH and water/solid ratio on the extraction yield of pomegranate seed oil using an aqueous extraction approach. In addition, quality indices, fatty acid composition and antioxidant activity of the obtained oil were studied and compared with those of typical hexane-, cold press- and hot press-extracted oil. Aqueous extraction resulted in the maximum oil recovery of 19.3% (w/w), obtained under the following critical values: water/solid ratio (2.2:1.0, mL/g), pH 5.0, extraction temperature = 63 °C and extraction time = 375 min. This yield is lower than that obtained via hexane extraction (26.8%, w/w) and higher than the yields from cold press (7.0%, w/w) and hot press (8.6%, w/w) extraction. A comparison of the characteristics of the oils based on extraction method revealed that the unsaturated fatty acid content was highest for the oil obtained by aqueous extraction. In addition, higher levels of iodine and peroxide and lower levels of acid, p-anisidine and unsaponifiable matter were observed. The oil obtained with aqueous extraction also exhibited higher antioxidant activity than oils obtained by hexane or hot press extraction.