Leaching calcium from phosphogypsum desulfurization slag by using ammonium chloride solution: Thermodynamics and kinetics study

Phosphogypsum(PG) desulfurization slag is a calcium-rich residue from reductive decomposition of PG using sulfur as the reductant. We proposed a technology of preparation light calcium carbonate with PG desulfurization slag, which mainly contains two steps: leaching and carbonizing. In this work, we concentrated on the former, in which ammonium chloride aqueous solution was utilized as leaching agent to extract calcium from the slag, and conducted thermodynamics and kinetics study on it. Fact Sage software was employed to do thermodynamic and phase equilibrium diagram calculations. The influence of leaching conditions including agitation speed, initial concentration of leaching solution, reaction temperature, and liquid/solid ratio on the calcium leaching rate was discussed in detail by means of experiment optimal design. A kinetic model developed from the shrinking core model was given to describe the leaching process. The apparent kinetic activation energy(Ea) of the leaching reaction was calculated to be 10.58 k J·mol~(-1).     

低品位铌钽矿高浓碱性介质浸出过程动力学研究

The leaching kinetics of niobium from a low-gr~te niobium-tantalum ore by concentrated KOH solution under atmospheric pressure has been studied. Significant effects of reaction temperature, KOH concentration,stirring speed, particle size and mass ratio of alkali-to-ore on the dissolution rate of niobium were examined. The experimental data of the leaching rates and the observed effects of the relevant operating variables were well interpreted with a shrinking core model under diffusion control. By using the Arrhenius expression, the apparent activation energy for the dissolution of niobium was evaluated. Finally, on the base of the shrinking core model, the rate equation was established.     

煤矸石盐酸浸溶出铝铁的动力学研究（英文）

The extraction of aluminum from coal mining waste (CMW) is an important industrial process. The two major problems in applications are low aluminum dissolution efficiency and high iron content in the raw material, which affect the quantity and quality of products. To improve the aluminum recovery process, the leaching kinet-ics of CMW with hydrochloric acid was studied. A shrinking core model was used to investigate aluminum and iron dissolution kinetics. Based on the kinetic characteristics, a process for recovering aluminum was proposed and tested experimental y. It is found that the aluminum leaching reaction is controlled by surface reaction at low temperatures (40–80 °C) and by diffusion process at higher temperatures (90–106 °C). The iron dissolution process is dominated by surface reaction at 40–100 °C. The results show that iron could be dissolved or separated by concentrated hydrochloric acid. Fine grinding wil improve aluminum dissolution significantly.     

MATHEMATICAL MODELING OF NON-CATALYTIC LIQUID-SOLID REACTION AND ITS SOLUTION BY ORTHOGONAL COLLOCATION

The mathematical model of non-catalytic liquid-solid diffusion reactions discussed in this paper can be applied to quite different cases. The models in the literature such as unreacted shrinking core model, two stage model and homogeneous model can be considered as special cases of the above model which has been derived for leaching vanadium from steel slag with sodium carbonate and]or sodium bicarbonate solution reacting with two components in the slag simultaneously. The vanadium leaching reaction is inhibited by the solid product formed during the reaction. The power law equation can be used to represent the kinetic experimental data of leaching reaction. The model equations have been solved by orthogonal collocation and semi-implicit Runge-Kutta method. The parameters of the model have been estimated by the complex method. The calculated results based on this model is in good agreement with experimental data.     

二氧化硫对石灰石的直接硫酸盐化作用的热重分析的研究与建模

The direct sulfation of limestone from different sources in Iran was studied in a thermogravimetric analyzer under atmospheric pressure. All limestone samples tested have higher than 97% CaCO3. Experimental conditions were as follows: particle size levels ranging from 1.6μm to 7.8μm, four level reaction temperatures (700°C,750°C, 800°C and 850°C), and two SO2 concentrations (2.4 × 10-3 and 3.2 × 10-3 mol.mol-i). The particle size and temperature showed dominant influences on the rate and level of conversion while the effect of SO2 concentration was weak. The shrinking core model can be used to describe the behavior of the sulfation process. The reaction kinetics and diffusion mechanism are both important in controlling the rate of the process. The two key parameters of the model, chemical rate constant Ks and effective diffusion coefficient Deff were obtained. Model predictions are in good agreement with the experimental data.     

Manganese leaching in high concentration flue gas desulfurization process with semi-oxidized manganese ore

Manganese leaching during high concentration flue gas desulfurization process with semi-oxidized manganese ore was studied in this paper. It was found that there were different reaction pathways among which MnO_2,Mn_2O_3 and MnCO_3 in semi-oxidized manganese ore during flue gas desulphurization and manganese leaching.High SO_2 concentration facilitated redox reaction between MnO_2 and SO_2, and high concentration of H_2SO_4 accelerated MnCO_3/Mn_2O_3 leaching from semi-oxidized ore. Kinetics study showed that manganese leaching in flue gas desulfurization process with semi-oxidized ore was controlled by a mixed-control model, that is the surface chemical reaction and mass diffusion dominated both the oxidation of SO_2 and manganese leaching process. The apparent activation energy was 13.05 k J·mol~(-1) and the reaction orders with respect to SO_2 and H_2SO_4 concentration were 1.38 and 0.10, respectively. Finally, a semi-empirical rate equation based on shrinking core model was derived to describe the process.     

Kinetics of lipase catalyzedenantioselective esterification of racemic ibuprofen in isooctane

The kinetics of Candida rugosa lipase catalyzed esteritlcation of racemic ibuprofen with n-butanol in isooctane was studied. The kinetic study was carried out with the addition of 0.1% and 2% (by volume) of water for enzyme activation respectively when celite was added into isooctane for enzyme dispersion. The specific initial rate for S-ibuprofen can be fitted with the Ping Pong Bi Bi mechanism with dead-end competitive inhibition by the alcohol. The time courses of the enantioselective esteriflcation of the two ibuprofen enantiomers with different initial substrate concentrations and water contents were simulated with a model in which both effects of enzyme inactivation by long term reaction and reversed hydrolytic reaction under high water content were taken into consideration.     

Application of the shrinking core model to the kinetics of zinc oxide desulfurization

The kinetics of H_2S removal by zinc oxide desulfurizer was studied through thermogravimetricanalysis.The experimental results show that desulfurization rate was controlled,at high temperatureand low conversion,by the chemical reaction rate,and at low temperature and high conversion by thegrain diffusion rate.The reaction is first order with respect to H_2S concentration in the differentcontrolled stages.The kinetic behavior can be modeled through the employment of the shrinking coremodel.The values of the model parameters were determined.The variation tendencies with temperatureand concentration of H_2S at the controlled stages were discussed.     

Leaching Kinetics of Calcium Vanadate by Na2CO3 Solution

Leaching kinetics of calcium vanadate by Na2CO3 solution was studied. Kinetic equation was established according to the variation of VO3-concentration with time during the leaching process. The influences of initial pH value and stirring speed on reaction rate constant were examined and the corresponding apparent activation energy was calculated. The results indicate that the leaching process is a 0.68 order reaction, and the reaction rate constant 8.64×10-6 mol/(L-s). It increases with the increase of pH value and stirring speed. And the dissolution rate of calcium vanadate also increases. The apparent activation energy is 38.98 kJ/mol, and temperature has great influence on the leaching rate of calcium vanadate.     

Effects of mechanical activation on the digestion of ilmenite in dilute H2SO4

The commercial sulfate process for pigment production uses concentrated sulfuric acid(N 85 wt% H_2SO_4) as feeding material and discharges 8–10 tons of spend dilute acid(20 wt% H_2SO_4) per ton of product. Re-using spend acid to leach ilmenite can cut the waste emission and save fresh feeding acid. However, the leaching reaction with dilute acid is very slow and the digestion efficiency is fairly low. This paper describes a wet-milling process to enhance the dilute-acid leaching of ilmenite that makes it possible to produce TiO_2 pigment in a more environmentally benign routine. The leaching kinetic study of unmilled ilmenite, dry milled 60 min ilmenite and wet milled 60 min ilmenite was conducted by revision of the shrinking core model(SCM), incorporation of particle size distribution(PSD) into SCM. The results revealed that mechano-chemical activation method significantly increased the leaching efficiency of titanium from 36% to 76% by reducing the particle size and increasing the reaction contact area. On the other hand, the milling process increased the lattice deformation and amorphization of crystalline, which lowered the activation energies in the leaching process. Compared with dry milling operation, wet milling is more effective, the particle size distribution of wet-milled ilmenite was much narrower, smaller, and more uniform. Wet milling of ilmenite makes the leaching reaction with dilute acid(60 wt% H_2 SO_4) practicable and the re-use of spend acid becomes possible and economical.     

糖蜜酒精废液中大分子焦糖色素模拟物浸出软锰矿的动力学

用收缩芯模型研究了糖蜜酒精废液中大分子焦糖色素在硫酸介质中还原浸出软锰矿的动力学,考察了软锰矿粒度、反应温度、浸出时间、硫酸浓度和焦糖色素浓度对锰浸出速率的影响.结果表明锰浸出速率随反应温度、硫酸浓度、焦糖色素浓度的增加和软锰矿粒径的减小而增加.糖蜜酒精废液中大分子焦糖色素还原浸出软锰矿属固体产物层扩散控制,表观活化能...     

软锰矿氧化脱色降解糖蜜酒精废液

采用软锰矿为氧化剂,在酸性条件下对糖蜜酒精废液进行氧化脱色降解,并同时浸出Mn。考察了反应温度、H2SO4浓度、软锰矿质量浓度等因素对糖蜜酒精废液脱色率、COD去除率和软锰矿中Mn浸出率的影响,并对反应过程机理进行了初步的探讨。结果表明,在Mn浸出量较小的情况下,即可获得较高的脱色率,而COD去除率却随Mn浸出量的增大而提高。在反应后期,部分有机物只能被氧化为有机酸,而不能进一步氧化为CO2。在反应温度90℃,H2SO4浓度1.1 mol/L,软锰矿质量浓度100 g/L,反应时间120 m in及采取二段反应工艺时,糖蜜酒精废液的脱色率可达98.2%,COD去除率达78.5%,软锰矿中Mn浸出率达到92.3%。     

Oxidative leaching kinetics of molybdenum-uranium ore in H2SO4 using H2O2 as an oxidizing agent

The processing of molybdenum-uranium ore in a sulfuric acid solution using hydrogen peroxide as an oxidant has been investigated. The leaching temperature, hydrogen peroxide concentration, sulfuric acid concentration, leaching time, particle size, liquid-to-solid ratio and agitation speed all have significant effects on the process. The optimum process operating parameters were: temperature: 95°C; H₂O₂ concentration: 0.5 M; sulfuric acid concentration: 2.5 M; time: 2 h; particle size: 74 μm, liquid-to-solid ratio: 14 ∶ 1 and agitation speed: 600 rpm. Under these experimental conditions, the extraction efficiency of molybdenum was about 98.4%, and the uranium extraction efficiency was about 98.7%. The leaching kinetics of molybdenum showed that the reaction rate of the leaching process is controlled by the chemical reaction at the particle surface. The leaching process follows the kinetic model 1 ? (1?X)^1/3 = kt with an apparent activation energy of 40.40 kJ/mole. The temperature, concentrations of H₂O₂ and H₂SO₄ and the mesh size are the main factors that influence the leaching rate. The reaction order in H₂SO₄ was 1.0012 and in H₂O₂ it was 1.2544.     

IN SITU LEACHING OF URANIUM USING DILUTE SULFURIC ACID AND MOLECULAR OXYGEN

The technical feasibility of in situ uranium leaching using dilute sulfuric acid and molecular oxygen has been assessed and the important process parameters examined by use of laboratory high pressure leaching columns.

The dilute H₂SO₄/O₂ lixiviant was effective in leaching uranium from the ore samples tested. The leaching process was chemical reaction rate limited and can be represented using pseudo first-order kinetics. The leaching rate constant is proportional to the proton concentration of the lixiviant.

Much of the uranium was leached from the ore before decomposition of carbonate minerals by the acid was complete. Acid consumption per pound of U₃O₈ increased sharply as the uranium recovery level exceeded 70%. There appears to be a minimum oxygen pressure for effective uranium leaching. A pressure of 2758 KPa was adequate for the ore samples tested     

废旧混合锂电池正极材料还原酸浸行为研究

针对废旧混合锂电池正极材料中有价金属元素镍钴锰的高效分离浸出,设计开发了2种不同混合废料体系：LiCoO₂与Li （Ni_1/3Co_1/3Mn_1/3） O₂、LiMn₂O₄与Li （Ni_1/3Co_1/3Mn_1/3） O₂,研究了还原剂用量、硫酸初始浓度、浸出温度、液固比对浸出过程的影响。LiCoO₂与Li （Ni_1/3Co_1/3Mn_1/3） O₂混合废料较适宜浸出参数为：浸出温度80℃、反应时间90 min、H₂SO₄浓度2.3 mol·L^-1,液固比R=8 mL·g^-1、还原剂Na₂SO₃用量=1.2倍理论量;LiMn₂O₄与Li （Ni_1/3Co_1/3Mn_1/3） O₂组成的混合废料的较适宜浸出实验参数为：浸出温度60℃、反应时间90 min、H₂SO₄浓度2.3 mol·L^-1,R=8 mL·g^-1、还原剂Na₂SO₃用量=1.2倍理论量。得到的浸出规律为混合锂离子电池正极废料回收工艺的广泛适应性提供了参考思路。     

汽车粉碎残渣中提取金属:不同浸出体系的初步实验结果(英文)

The study is focused on the extraction of valuable metals from automotive shredder residue (ASR) by different leaching solutions. First, ASR samples were roasted at 600 °C to simulate a thermal treatment processing. Distil ed water, citric and sulphuric acid were preliminarily investigated, thus two further full factorial systems entailing H2SO4–H2O2 and H2SO4–H2O2–Fe3+ were tested. The preliminary experimental results showed that 0.1 mol·L?1 H2SO4 solution extracted 100%of Cu, Fe and Zn, whereas citric acid leached 100%of Zn and Pb, 59%of Fe and 62%of Cu;whereas, H2SO4–H2O2 and H2SO4–H2O2–Fe3+(Fenton's) leaching media showed that Cu, Fe and Zn can be extracted simultaneously and completely from the ASR ashes before final disposal.     

废糖蜜-硫酸溶液中软锰矿的浸出动力学

用收缩芯模型研究了硫酸介质中废糖蜜还原浸出软锰矿的动力学,考察了软锰矿粒度、反应温度、浸出时间、硫酸浓度和废糖蜜浓度对锰浸出速率的影响. 结果表明,提高反应温度、硫酸浓度、废糖蜜浓度和减小软锰矿颗粒的初始平均半径,均可提高锰的浸出速率. 废糖蜜还原浸出软锰矿属界面化学反应控制,表观活化能为45.6 kJ/mol,硫酸和废糖蜜的反应级数分别为0.52及0.28.     

新型纳米SO42-/TiO2催化剂制备及催化合成醋酸丁酯

采用高压水热法合成纳米锐钛矿相TiO₂前驱体,通过H₂SO₄溶液浸渍制备系列新型SO₄^2-/TiO₂催化剂,采用XRD、TG-DTG和TEM对其结构和形貌进行表征,并用于催化醋酸与正丁醇的酯化反应,考察H₂SO₄溶液浓度、浸渍时间和反应时间对酯化率的影响。结果表明,在H₂SO₄浓度1 mol·L^-1、浸渍时间12 h和反应时间180 min条件下,酯化率高达99.2%,催化剂具有优异的催化性能和较佳的重复使用性。