硫酸-糖蜜酒精废液浸出软锰矿的动力学(英文)

The kinetics of reductive leaching of manganese from low grade pyrolusite in dilute sulfuric acid in the presence of molasses alcohol wastewater was investigated. The shrinking core model was applied to quantify the effects of reaction parameters on leaching rate. The leaching rate increases with reaction temperature, concentrations of H 2 SO 4 and organic matter in molasses alcohol wastewater increase and ore particle size decreases. The leaching process follows the kinetics of a shrinking core model and the apparent activation energy is 57.5 kJ·mol –1 . The experimental results indicate a reaction order of 0.52 for H2SO4 concentration and 0.90 for chemical oxygen demand (COD) of molasses alcohol wastewater. It is concluded that the reductive leaching of pyrolusite with molasses alcohol wastewater is controlled by the diffusion through the ash/inert layer composed of the associated minerals.     

硫酸盐熔融反应法从钛铁矿中提取钛的研究

以海南万宁的钛铁矿和硫酸铵为主要原料,通过熔融反应法使钛铁矿中的钛转化为易溶于稀酸的硫酸氧钛,用稀硫酸浸取,达到提高钛浸取率的目的。考察了硫酸铵加入量、焦硫酸钾加入量、反应温度、稀硫酸浸取浓度对钛浸取率的影响。实验结果表明：硫酸铵和焦硫酸钾的加入量、反应温度对钛浸取率的影响较大。提高钛浸取率的最佳条件为：m（钛铁矿）∶m（硫酸铵）∶m（焦硫酸钾）=1∶6∶0.5,反应温度为450 ℃,保温时间为30 min,稀硫酸浸取浓度为2.32 mol/L,在此条件下钛的浸取率达到96.82%。     

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。     

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.     

双氧水法脱硫副产稀硫酸浓度的探讨

介绍了双氧水脱硫的基本原理,阐述了维持H2O2一定浓度的必要性,分析了稀硫酸浓度对SO2脱除率、气相中硫酸雾含量的影响,提出了适宜的控制浓度.双氧水法脱硫的稀硫酸w(H2SO4)一般不宜超过30％,w(H2O2)控制在0.3％～0.5％,硫磺制酸企业稀硫酸w(H2SO4)可适当降低至20％～25％.     

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.     

Simultaneous preparation of TiO2 and ammonium alum,and microporous SiO2 during the mineral carbonation of titanium-bearing blast furnace slag

In this study, a route for simultaneous mineralization of CO₂ and production of titanium dioxide and ammonium alum, and microporous silicon dioxide from titanium-bearing blast furnace slag (TBBF slag) was proposed, which is comprised of (NH₄)₂SO₄ roasting, acid leaching, ammonium alum crystallization, silicic acid flocculation and Ti hydrolysis. The effects of relevant process parameters were systematically investigated. The results showed that under the optimal roasting and leaching conditions about 85% of titanium and 84.6% of aluminum could be extracted while only 30% of silicon entered the leachate. 84% of Al³⁺ was crystallized from the leachate in the form of ammonium aluminum sulfate dodecahydrate with a purity up to 99.5 wt%. About 85% of the soluble silicic acid was flocculated with the aid of secondary alcohol polyoxyethylene ether 9 (AEO-9) to yield a microporous SiO₂ material (97.4 wt%) from the crystallized mother liquor. The Al- and Si-depleted solution was then hydrolyzed to generate a titanium dioxide (99.1 wt%) with uniform particle size distribution. It was figured out that approximately 146 kg TiO₂ could be produced from 1000 kg of TBBF slag. Therefore, the improved process is a promising method for industrial application.     

Catalytic performance of sulfonic acid functionalized ionic liquids on preparation of biodiesel

通过1-烯丙基咪唑与1,4-丁基磺酸内酯反应制备的两性离子分别与硫酸、三氟甲基磺酸、磷钨酸、磷钼酸和硅钨酸直接反应制备了5种磺酸功能化离子液体。采用¹H NMR、FTIR、TG/DTA等技术手段对其结构及热稳定性进行了表征。最后通过催化油酸与甲醇酯化反应制生物柴油过程对催化剂的催化活性和重复使用性进行了评价。结果表明,5种离子液体均具有高催化活性（高于浓硫酸）,并且重复使用4次后,催化活性基本保持不变。3种杂多酸离子液体不溶于产物,以固态形式与产物混合,为其回收和重复利用提供了有利条件。     

A STUDY OF H2SO4 FORMATION IN THE PROCESS OF SIMULTANEOUS SORPTION OF SO2, O2 AND H2O ONTO A SINGLE CARBON PARTICLE

A mathematical model to describe simultaneous sorption of SO₂, O₂ and H₂O in an activated carbon particle is presented in this paper. The competition for active sites of these species is taken into account by a modified Langmuir-type isotherm, which incorporates the competition of the immobile reaction product phase, H₂SO₄. Simulations of the model are presented in terms of transient micropore filling of reactant species and product H₂SO₄. The simulation results show that the multicomponent interactions play an important role in the sorption process. Fast diffusing species like O₂ and H₂O instantaneously adsorb in the micropore volume of the sorbent. In the course of simultaneous adsorption and reaction of all species in the micropore, a rollup phenomenon on the transient behavior of fast diffusing species could occur, i.e. the micropore loading of these gaseous species can overshoot the final equilibrium level. The simulation results of H₂SO₄ micropore loading are found to agree reasonably well with the experimental data.     

Formation of nanometric hard materials by cold milling

The fabrication of nanosized, single crystal TiC or TiN powders from ilmenite or TiO₂ within a single low temperature stage is reported in this paper. The titaniferous powders were ball milled for 100 h in a laboratory scale mill with magnesium powder and either graphite or nitrogen. The resultant powders were then subjected to an annealing step at 1200°C. Differential thermal analysis and X-ray diffraction showed that the phases formed within the milling step and underwent grain growth on annealing. Acid leaching of the powders selectively removed the unwanted product phases leaving only the hard material. The final particle size and Scherrer XRD crystallite size were similar after annealing, implying that the particles produced were single crystal.     

酸浸法提取粉煤灰中氧化铝溶出规律的研究

酸浸法是粉煤灰提铝的主要方法之一。介绍了一种提取粉煤灰中氧化铝的方法,用不同浓度的硫酸作溶剂,用氟化钠作助溶剂,通过一定配比加入粉煤灰中反应。实验结果表明,当温度为沸腾温度、氟化钠添加量为0、硫酸浓度为12 mol/L、溶出时间为150 min时,氧化铝的溶出率可达80.19%。该工艺反应在低温常压下进行,避免了高温烧结工艺,节约了能源,降低了成本,具有较高的实用价值。     

Effective regeneration of thermally deactivated commercial V-W-Ti catalysts

An effective method for the regeneration of thermally deactivated commercial monolith SCR catalysts was investigated. Two types of regenerated solutions, namely NH₄Cl (1 mol/L) and dilute H₂SO₄ (0.5 mol/L), were employed to treat the used catalyst. The effects of temperature and the regeneration process on the structural and textural properties of the catalysts were determined by X-ray diffraction, scanning electron microscopy, N₂ adsorption/desorption, elemental analysis and Fourier transform infrared spectroscopy. The results suggest that the anatase phase of the used catalyst is maintained after exposure to high temperatures. Some of the catalytic activity was restored after regeneration. The catalyst regenerated by aqueous NH₄Cl had a higher activity than that of the catalyst treated by dilute H₂SO₄. The main reason is that the NH₃ generated from the decomposition of NH₄Cl at high temperatures can be adsorbed onto the catalyst which promotes the reaction. The aggregated V₂O₅ were partially re-dispersed during the regeneration process, and the intrinsic oxidation of ammonia with high concentrations of O₂ is a factor that suppresses the catalytic activity.     

电场强化铁粉还原对苯醌合成对苯二酚

研究了在酸性体系中,用电场强化铁粉还原对苯醌制对苯二酚的方法,该法考察了铁粉用量、硫酸用量、硫酸加入方式、电解电压和反应时间对铁粉利用率与对苯二酚收率的影响,并在此基础上探讨了还原机理。结果表明:电场强化了还原反应过程中电子的定向迁移,活化了反应物。此时,在95℃下,当硫酸与铁粉的摩尔比n(硫酸):n(铁粉)=1:3,采用逐步加入硫酸的方式,电解电压为3.0V,反应时间为2h时,铁粉利用率由28.57%提高到75.19%,对苯二酚收率达95%。与现有工艺相比,电场强化法的铁粉利用率高、还原过程无副产物,并且该法易于控制,反应周期短。     

废锌催化剂的铵盐浸出工艺

废锌催化剂是一种含锌废弃物,可采用铵盐浸出工艺回收其中的锌资源。具体步骤：对废锌催化剂先进行预处理,以氯化铵为浸取剂,经浸取反应、过滤分离得到氯化锌溶液。实验得到适宜的工艺条件：废锌粒度为58~ 80 μm、氯化铵质量分数为17%、反应温度为60 ℃、反应时间为2 h。在此条件下,锌浸出率达95.2%,镍残存率为0.7%,实验证实了氯化铵溶液作为浸取剂的优势。XRD测试表明,前驱体为Zn₄CO₃（OH）₆·H2O,得到的样品是氧化锌粉体,粉体粒径为63 nm,纯度为99.3%。     

Chemical dehydration coupling multi-effect evaporation to treat waste sulfuric acid in titanium dioxide production process

In order to concentrate the diluted sulfuric acid from the titanium dioxide(TiO_2) production of sulphate process,a new concentration process was proposed by coupling chemical dehydration and multi-effect evaporation. The ferrous sulfate monohydrate(FeSO_4·H_2O), as the dehydrant, was added to the diluted sulfuric acid to form ferrous sulfate heptahydrate(FeSO_4·7H_2O) according to the H_2SO_4-FeSO_4-H_2O phase diagrams, which partially removes the water. This process was named as Chemical Dehydration Process. The residual water was further removed by two-effect evaporation and finally 70 wt% sulfuric acid was obtained. The FeSO_4·H_2O can be regenerated through drying and dehydration of FeSO_4·7H_2O. The results show that FeSO_4·H_2O is the most suitable dehydrant, the optimal reaction time of chemical dehydration process is 30 min, and low temperature is favorable for the dehydration reaction. 45.17% of the entire removed water can be removed by chemical dehydration from the diluted sulfuric acid. This chemical dehydration process is also energy efficient with 24.76% saving compared with the direct evaporation process. Furthermore, 51.21% of the FeSO_4 dissolved originally in the diluted sulfuric acid are precipitated out during the chemical dehydration, which greatly reduces the solid precipitation and effectively alleviates the scaling in the subsequent multi-effect evaporation process.     

反应结晶过程中二水硫酸钙晶粒性能

设计了CaHPO₄·2H₂O-H₂SO₄-H₃PO₄-H₂O体系结晶温度、液相SO₄^2-含量、液相P₂O₅含量、搅拌速率和结晶时间的五因素四水平正交实验,通过测量晶体平均粒径优化出平均粒径最大的工艺参数:结晶温度80℃、液相SO₄^2-含量50g·L^-1、液相P₂O₅含量260g·L^-1、搅拌速率50r·min^-1和结晶时间2h。在该工艺参数下进行结晶过程研究,通过分析液相SO₄^2-浓度和P₂O₅浓度,XRD、SEM、EDS和激光粒度分析仪表征晶体,研究发现:0~40min为反应阶段,平均粒径减小;40min之后结晶过程遵从Ostwald递变法则,从CaSO₄·0.5H₂O过渡到CaSO₄·2H₂O,平均粒径几乎不变。     

Formation of Nanometric TiB2 from TiO2

Titanium diboride can be produced by ball-milling a mixture of TiO₂, B₂O₃, and Mg metal for between 10 and 15 h. The reaction was found to be completed during the milling with no evidence of residual Mg. The unwanted phase, MgO, was readily removed by leaching in acid. The leached powder obtained after 15 h milling had a particle size of <200 nm and was highly faceted. The particle size decreased to ∼50 nm after 100 h milling and seemed to be relatively monodisperse. Scherrer calculation of the crystallite size showed that the product particles were probably single crystal.     

双极膜电渗析法连续制备聚合硫酸铁

研究了双极膜电渗析法连续制备聚合硫酸铁（PFS）的工艺。主要考察了电流密度、原料补充液中硫酸亚铁和硫酸的摩尔比以及原料补充液流速对产品PFS各性能指标（盐基度、全铁含量、pH、密度等）和过程能耗的影响。研究结果表明：电流密度从10mA/cm²增加到20mA/cm²时,盐基度从8.59%显著增加到11.32%,去浊率从84.31%逐渐增加到95.34%,但当电流密度大于20mA/cm² 时,盐基度和去浊率稍有下降,过程能耗最高可达4.26kW·h/kg H₂SO₄,酸液罐酸浓度最高可达0.45mol/L;原料补充液中硫酸亚铁和硫酸的摩尔比从2.01增加到4.08时,盐基度从8.69%增加到11.38%,去浊率从94.96%逐渐增加到95.88%,能耗在3.05~3.15kW·h/kg H₂SO₄ 范围内变化,酸液罐酸浓度约为0.38mol/L;原料补充液流速从1mL/min增加到3mL/min时,盐基度从11.52%下降到6.75%,去浊率从95.92%逐渐降低到75.61%,同时,能耗从3.09kW·h/kg H₂SO₄下降到2.77kW·h/kg H₂SO₄。