An investigation on dissolution kinetics of single sodium carbonate particle with image analysis method

Dissolution kinetics of sodium carbonate is investigated with the image analysis method at the approach of single particle. The dissolution experiments are carried out in an aqueous solution under a series of controlled temper-ature and pH. The selected sodium carbonate particles are al spherical with the same mass and diameter. The dissolution process is quantified with the measurement of particle diameter from dissolution images. The concentration of dissolved sodium carbonate in solvent is calculated with the measured diameter of particle. Both surface reaction model and mass transport model are implemented to determine the dissolution mecha-nism and quantify the dissolution rate constant at each experimental condition. According to the fitting results with both two models, it is clarified that the dissolution process at the increasing temperature is controlled by the mass transport of dissolved sodium carbonate travelling from particle surface into solvent. The dissolution process at the increasing pH is control ed by the chemical reaction on particle surface. Furthermore, the dissolution rate constant for each single spherical sodium carbonate particle is quantified and the results show that the disso-lution rate constant of single spherical sodium carbonate increases significantly with the rising of temperature, but decreases with the increasing of pH conversely.     

中国在环境友好浸取过程方面的一些研究

The newly developed green leaching processes for chromium, lead and gold extraction from ores or concentrates are described. The chromium is extracted from the iron chromite ore with fused sodium hydroxide at 500---550~C as sodium chromate. The galena in lead sulfide concentrate is converted into lead carbonate in ammonium or sodium carbonate solution at 50---80℃ followed by the separation of lead carbonate formed from the unconverted sulfide ores by flotation. Gold associated with sulfide ore (such as pyrite and chalcopyrite) can be extracted into sodium thiceulfate solution without any pretreatment such as roasting, high pressure aqueous oxidation or bacteria pre-leaching.     

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).     

膜电解法再生碳酸钾脱碳溶液(英文)

In this work, the regeneration mechanism of potassium carbonate solution after absorption of CO2 using ion-exchange membrane electrolysis was presented. The solutions of potassium carbonate (K2CO3) and potassium bicarbonate (KHCO3) were used to simulate the solution after absorbing CO2. Experiments were carried out at various electrodes, temperatures and current densities. The results indicate that the membrane electrolysis can increase concentration ratio of K2CO3 and KHCO3, and achieve 100% conversion. In this process, not only CO2 is desorbed from carbonate solution, but also hydrogen, as a byproduct, is generated at the cathode, which is the main contributor to reduce energy consumption. Thus, the membrane electrolysis is valuable in the regeneration of the K2CO3 absorbent.     

Separation of chitin from shrimp shells enabled by transition metal salt aqueous solution and ionic liquid

Chitin is a widely used important industrial polymer mainly from shrimp shells, but its commercial preparation is under the great challenge of serious pollution due to the requirement of HCl and Na OH.Herein, we demonstrated that high purity chitin can be obtained from waste shrimp shells(WSSs) by cascade separation with transition metal salt aqueous solution and ionic liquid(IL). Firstly, calcium carbonate of WSSs was effectively removed in the metal salt aqueous solution driven by the ion exch...     

纳米碳酸钙在非等温条件下热分解动力学及机理研究

Experiments on thermal decomposition of nano-sized calcium carbonate were carried out in a thermo-gravimetric analyzer under non-isothermal condition of different heating rates (5 to 20K·min-1). The Coats and Redfern's equation was used to determine the apparent activation energy and the pre-exponential factors. The mechanism of thermal decomposition was evaluated using the master plots, Coats and Redfern's equation and the kinetic compensation law. It was found that the thermal decomposition property of nano-sized calcium carbonate was different from that of bulk calcite. Nano-sized calcium carbonate began to decompose at 640℃, which was 180℃lower than the reported value for calcite. The experimental results of kinetics were compatible with the mechanism of one-dimensional phase boundary movement. The apparent activation energy of nano-sized calcium carbonate was estimated to be 151kJ·mol-1 while the literature value for normal calcite was approximately 200kJ·mol-1. The order of magnitude of pre-e     

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.     

DBU-based CO_2 absorption–mineralization system: Reaction process,feasibility and process intensification

Amine-based carbon dioxide(CO_2) capture is still limited by high desorption energy consumption. Fixing CO_2 into carbonate is a safer and more permanent method. In this work, calcium oxide(CaO) is introduced to perform chemical desorption instead of thermal desorption on 1,8-diazabicyclo [5.4.0] undec-7-ene(DBU) aqueous solution after CO_2 absorption. The X-ray diffraction(XRD) patterns of solid products show the formation of calcite calcium carbonate(CaCO_3), which prove the feasibility of this method. The effects of reaction temperature, reaction time and Ca~(2+)/CO_3~(2-) molar ratios on the related reactions in CO_2 absorption–mineralization process and CaCO_3 precipitation are discussed, and purer CaCO_3 is obtained by ultrasonic treatment. The CaCO_3 content can be increased to 95.8% and the CO_2 desorption ratio can achieve 80% by 30 min ultrasonic dispersion treatment under the conditions(40℃, 180 min, Ca~(2+)/CO_3~(2-) molar ratio = 1.0). After five cycles, DBU aqueous solution shows stable CO_2 absorption and mineralization ability. Fourier transform infrared spectroscopy(FT-IR) spectra of the reaction process also indicate the regeneration of the solvent. Compared with thermal desorption, this process is exothermic, almost without no additional heat.     

The Effects of Oxidative Pretreatment of Zinc-containing Dust on Contents of Iron and Manganese in Ammoniacal Leaching Solution and Product ion of Zinc Oxide

The zinc-containing dust was oxidatively pretreated with calcium hypochlorite,subsequently leached with ammonia/ammonium bicarbonate solution to obtain the ammoniacal leaching solution,and zinc oxide was produced by ammonia distillation of the ammoniacal leaching solution and subsequent calcination. The elements of iron and manganese could not be detected in ammoniacal leaching solution,and the extraction rate of zinc was 98.2% in ammoniacal leaching process. The zinc oxide content in the product is 99.5%(ω),and the contents of iron and manganese in the product were 0.002 8‰ and 0.000 84‰(ω), respectively. The analyses of the valence states of iron and manganese in the zinc-containing dust with and without pretreatment were performed by chemical analysis and XPS,and the possible oxidation mechanism of the oxidative pretreatment of the dust was discussed. It is concluded that Fe 2+-oxide and Mn 2+-oxide in the dust were oxidized to Fe 3+-oxide and/or its hydrate and Mn 4+-oxide and/or its hydrate by calcium hypochlorite during the oxidative pretreatment process,respectively.     

芒硝制纯碱和硫酸新工艺探讨

我国芒硝储量世界第一,大部分位于欠发达的西部地区,芒硝还是许多工业过程的副产物,大多含有环境污染物.芒硝本身利用价值低,市场容量小,开发新的利用途径具有重要意义.提出了一种芒硝制纯碱和硫酸的新工艺,它是以氧化钙和重铬酸钠水溶液为转化介质,硫酸钠先和氧化钙在重铬酸钠水溶液中反应,得到硫酸钙沉淀和铬酸钠水溶液,前者高温还原分解再生氧化钙,同时得到二氧化硫和二氧化碳,二氧化硫经转化吸收得硫酸;后者和二氧化碳反应再生重铬酸钠水溶液,同时得到碳酸氢钠沉淀,碳酸氢钠经脱铬处理制得纯碱.该工艺借鉴了工业上成熟的石膏分解制硫酸技术和铬酸钠碳化制重铬酸钠技术,具有成本低、腐蚀轻、无废物排放等特点,有望为我国丰富的芒硝资源开辟新的应用途径.     

重铬酸钠溶液分解碳酸钙制取铬酸钙

介绍了一种制取铬酸钙的新方法,利用重铬酸钠溶液分解碳酸钙,可以得到高纯度的铬酸钙. 实验表明,温度和浓度是影响碳酸钙分解的关键因素,当重铬酸钠浓度大于60%、重铬酸钠与碳酸钙摩尔比大于1.05:1时,常压沸腾条件下即可完全分解碳酸钙,制得纯度99.5%的铬酸钙,收率接近100%. 分解过程中产生的二氧化碳气体可用于碳化分离铬酸钙后的铬酸钠溶液再生重铬酸钠,循环利用. 新方法工艺简单、产品纯度和收率都较高,无环境污染.     

磷石膏综合利用副产物碳酸钙渣的再资源化

对磷石膏两步法制备硫酸钾的副产物碳酸钙渣的处置技术进行了研究。以盐酸浸取碳酸钙渣制备氯化钙,选用碳酸氢铵和氨水为碳化剂对氯化钙深加工制备碳酸钙;碳酸钙渣得到再资源化,避免再次废弃污染环境,进一步深化磷石膏的综合利用。     

用天然石膏制备硫酸铵和氯化钙的工艺研究

以天然石膏和碳酸氢铵为原料进行复分解反应制备硫酸铵,副产碳酸钙粗品。考察了反应温度、反应时间、配料比、液固比等因素对硫酸钙转化率的影响,通过正交实验确定了复分解反应的最佳工艺条件。探讨副产物碳酸钙的回收利用方法,用盐酸处理碳酸钙粗品制备氯化钙,研究确定了工艺条件。整个生产过程无废渣排放,工艺简单清洁。通过本方法,可将天然石膏转化为具有更高价值的硫酸铵和氯化钙,研制的产品质量达到有关标准,应用前景广阔。     

盐硝联产芒硝水不溶物的产生与控制

针对真空制盐-盐硝联产五效蒸发工艺中芒硝所含水不溶物的含量过多、导致卤水浊度超标影响芒硝质量的问题,研究分析水不溶物产生的源头,找出控制水不溶物生成的方法具有重要意义。采用X射线衍射（XRD）、电子扫描显微镜（SEM-EDS）和红外光谱分析（FT-IR）等分析手段对芒硝中水不溶物的物相组成和形貌特性进行分析,确定芒硝水不溶物主要成分为方解石型碳酸钙。发现水不溶物形成的主要原因是盐系统中的钙离子浓度过高,此时溶液过饱和度高、处于不稳定状态,碳酸钙析出较快,结晶数目较多、颗粒小。小颗粒的碳酸钙漂浮在循环母液中通过转卤进入硝系统,与硝系统本身产生的碳酸钙相加导致芒硝中水不溶物的含量超标。针对此问题提出了源头调控的方案。在净化过程中当碳酸钠的质量浓度由1.32 g/L调整为1.35~1.38 g/L时,可以控制卤水中钙离子与碳酸根的平衡,降低盐、硝系统中的钙离子浓度,进而达到控制水不溶物的含量。在新一轮工业化生产中,采用源头调控的方法对芒硝中水不溶物进行了有效控制,芒硝质量得到了明显提升。     

以可溶性淀粉为晶型调控剂制备多孔球形碳酸钙

利用简单易行的复分解反应,以氯化钙和碳酸钠为合成试剂,以可溶性淀粉（SS）为晶型调控剂,制备出以球霰石晶型为主的碳酸钙多孔微球。通过单因素条件实验,分别考察可溶性淀粉添加量、碳酸钠溶液滴加速度、氯化钙与碳酸钠的物质的量比对碳酸钙形貌和晶型的影响。利用X射线衍射仪（XRD）,扫描电子显微镜（SEM）对其晶型、形貌进行表征。研究表明当SS添加量为0.5 g,滴加速度为1.5 mL/min,氯化钙与碳酸钠的物质的量比为1∶1时,可制备获得4~5 μm的多孔球霰石碳酸钙。     

渤海莱州湾地下卤水纳滤过程的结垢趋势研究

针对莱州湾地下卤水纳滤过程中纳滤膜表面无机物结垢的问题,利用饱和度法系统研究了碳酸钙、硫酸钙在卤水体系和纳滤过程中的结垢趋势和影响因素。结果表明,在常温下原料卤水中的碳酸钙处于饱和状态,而其中的硫酸钙处于不饱和状态,因此在外部因素诱导下,碳酸钙更容易发生沉淀;降低卤水的pH可以有效抑制碳酸钙结垢;当逐步提高卤水的产水回收率时,纳滤浓水侧卤水中硫酸钙结垢的风险增大,在纳滤精制卤水过程中选择合适的产水回收率可以降低硫酸钙结垢的风险。     

用硝酸磷肥生产中副产的磷石膏制备硫酸铵和碳酸钙

随着磷矿品位的不断下降,磷复肥企业必然面对使用中低品位的磷矿。为了解决冷冻法硝酸磷肥生产中深度除钙副产磷石膏的堆积问题,以磷石膏、碳酸铵和氨水为原料进行复分解反应制备硫酸铵和碳酸钙,以实现硫资源的循环利用。考察了影响硫酸钙转化率的各种因素,通过正交实验确定了复分解反应的优惠工艺条件,并作了验证性实验。结果表明,在优惠工艺条件下磷石膏中硫的转化率可达96.7%。用磷石膏生产硫酸铵,不仅是环境保护的需要,也是废物利用、资源回收的需要,具有潜在的社会效益和经济效益。     

AA/APES阻垢剂的合成及性能研究

以丙烯酸(AA)、烯丙氧基聚乙氧基硫酸铵(APES)为原料,过硫酸铵为引发体系,在水溶液中合成了AA/APES共聚物阻垢剂。考察了共聚物单体摩尔配比、阻垢剂用量对阻碳酸钙、磷酸钙垢率的影响,并与其它阻垢剂进行了比较。结果表明,AA/APES具有良好的阻碳酸钙和磷酸钙垢性能。     

高密度类球形碱式碳酸镍快速制备工艺研究

根据HG/T 4696—2014《工业碱式碳酸镍》的质量要求,研究开发出一条制备工艺简便且易实现产业化的高密度碱式碳酸镍生产工艺。研究了一种加压喷雾的方式进料、使得物料在反应系统内更加均匀、易形成大颗粒、从而提高碱式碳酸镍产品松装密度的制备工艺。通过探究反应温度、反应pH、硫酸镍浓度、碳酸钠浓度、反应转速对松装密度的影响,寻找出影响较大的工艺条件开展正交实验,得出最佳工艺条件：40 ℃条件下,采用镍离子质量浓度为100 g/L的硫酸镍溶液加压喷雾法进料,用106 g/L碳酸钠溶液在自动控制系统下控制反应pH为8.0左右,反应过程中反应转速控制在300 r/min,即可制备出松装密度为0.7 g/cm³以上、杂质含量低且形状为类球形的碱式碳酸镍产品。