Continuous changes in electrical conductivity of sodium aluminate solution in seeded precipitation

The mechanism of seeded precipitation of sodium aluminate solution was studied by measuring the seeded-precipitation rate and electrical conductivity online, as well as calculating the activity and fraction of ion pair. The results show that the electrical conductivity of sodium aluminate slurry linearly decreases with increasing aluminum hydroxide addition. Moreover, both the electrical conductivity of slurry and the difference in electrical conductivity between sodium aluminate solution and slurry remarkably decline in the first 60 min before gradually increasing in the preliminary 10 h and finally reaching almost the same level after 10 h. In low Na2 O concentration solution the activities of Na OH and Na Al（OH）4 in seeded precipitation are high, which can enlarge the difference in conductivity between slurry and solution. Additionally, more ion pairs exist in solution in preliminary seeded precipitation, and the adsorption of Na＋Al（OH）4- on seed surface is likely to break the equilibrium of ion pair formation and to decrease the difference in conductivity in preliminary seeded precipitation.

Intensifying gibbsite precipitation from sodium aluminate solution by adding a mixed seed

Gibbsite precipitation from sodium aluminate solution was intensified by adding mixed industrial and self-prepared active seeds,and its mechanism was researched preliminarily.The interfacial properties of seed/aluminate solution were determined for separate industrial and active seed.Contact angles of seed/aluminate solution and the specific surface area of seeds were respectively measured by sessile drop and BET method,and the morphology and particle size of precipitates were recorded by SEM and laser diffraction.The results show that,compared with the industrial seed,the active seed has a better wettability,lower interfacial tension,and larger specific surface area,being conducive to enhancing gibbsite precipitation from sodium aluminate solution.SEM analysis of the precipitates indicates that the embedment and accumulation/agglomeration of extremely fine particles on the surface of coarse industrial seed can effectively control the content of fine particles in the precipitation product.With extra 3.1–4.6 g/L active seed,the gibbsite precipitation ratio was increased by 3.23%–3.92%.Moreover,the mass percentage of particles<45μm in precipitation product has even a slight decrease compared with that for the traditional precipitation product or of the industrial seed itself.The result presented is favorable to developing an intensified gibbsite precipitation process for commercial alumina manufacture.

Periodical attenuation of Al(OH)_3 particles from seed precipitation in seeded sodium aluminate solution

Periodical attenuation of particles,which interferes seriously the normal alumina production,exists in Bayer process.In order to solve this problem,the rule of periodical attenuation of Al(OH) 3 particles was investigated by laboratory experiments under simulated industrial conditions.The results show that at higher temperature the variation period of particle size is shortened,while prolongs with more solid content.Particle size fluctuation amplitude reduces with the temperature rising but increases with the solid content increasing.Particle size distribution becomes more uniform by replenishing fine seeds,enabling the periodical fluctuation of Al(OH)3 particle size to be attenuated.Combining properly the additives with controlling the seed size is able to reduce the amplitude of periodical fluctuation and shorten the attenuation time.With unbalance of particle size distribution,the particles gradually become bigger,even inducing the decrease of the specific surface area of seeds,which is the major reason causing explosive attenuation of Al(OH)3 particles in seed precipitation process.

Effect of lithium ion on seed precipitation from sodium aluminate solution

Effect of lithium ion in sodium aluminate solution on precipitation rate,lithium content,morphology,and crystallization of alumina trihydrate(ATH) was investigated. Results showed that increasing lithium ion concentration in solution improved the precipitation rate and lithium content in ATH,whereas reduced the mass fraction of lithium precipitation from solution. Lithium ion in solution generated the fine ATH, and thereafter significantly increased the total particle number due to the preferential nucleation.Elevating temperature or reducing lithium ion concentration decreased lithium content in ATH and reduced the fine particle amount.Moreover, lithium ion in the solution changed the morphology of ATH by improving the growth of the(110) and(200) planes of gibbsite.A large amount of fine bar-or flake-shaped ATH attached on the coarse particles also benefited the secondary nucleation and led to the poor strength of alumina.All results will further contribute to improving the quality of alumina.

Model of apparent crystal growth rate and kinetics of seeded precipitation from sodium aluminate solution

Based on the population balance equation in a batch crystallizer characteristic of seeded precipitation, a model to calculate the rate of apparent crystal growth of aluminum hydroxide from the size distribution was deve- loped. The simulation results indicate that the rate of apparent crystal growth during seeded precipitation exhibits a manifest dependence on the crystal size. In general, there is an obvious increase in the apparent crystal growth rate with the augment in crystal size. The apparent activation energy increases with the increase of characteristic crystal size, which indicates that the growth of small crystals is controlled by surface chemical reaction; it is gradually controlled by both the surface reaction and diffusion with the augment in crystal size.

Effects of Na_4EDTA and EDTA on seeded precipitation of sodium aluminate solution

Na4EDTA and EDTA were adopted as new additives to intensify the seeded precipitation process of sodium aluminate solution. The effects of the two additives at certain concentrations on the seeded precipitation rate of sodium aluminate solution, particle size distribution (PSD) and morphology of precipitated gibbsite were investigated using titration method, particle size analyzer and scanning electron microscope (SEM), respectively. The results show that the two additives can accelerate the seeded precipitation rate of sodium aluminate solution. At relatively high concentration, the facilitative effect of EDTA on sodium aluminate solution is more obvious than that of Na4EDTA. EDTA makes gibbsite particles thinner than Na4EDTA. The Na+ and H+ result in the different effects on the seeded precipitation rate of sodium aluminate solution in spite of the same EDTA anion in the two additives.

Phenomena in late period of seeded precipitation of sodium aluminate solution

Aiming at seeded precipitation of aluminate solution with high caustic ratio(αk>2.4), corresponding to the late period of seeded precipitation, the influence of different types of seed on precipitation ratio was explained with respect to solution structure in the interface of seed and the evolution of Al(OH)3 growth units in this layer. The effects of solid content and seed size on agglomeration were determined by calculating the particle number of product. The results imply that the solution structure in the interface of seed imposes a notable significance on the process in the late period of seeded precipitation. Agglomeration still exists in this period. However, the agglomeration bodies break in the case of prolonging precipitation due to the mechanical effect, which results in the increase of particle number.

Preparation of Al(OH)_3 by ion membrane electrolysis and precipitation of sodium aluminate solution with seeds

The preparation of Al(OH)3 by the ion exchange membrane electrolysis followed by the precipitation of sodium aluminate solution with seeds was made. During the process of ion membrane electrolysis, the sodium aluminate solution is rapidly acidified and the caustic ratio (aK) is decreased due to oxygen evolution in the anodic region. And the causticity of solution is increased due to hydrogen evolution in the cathode region, producing the high concentration of caustic soda solution. Regulating the acidity of the anodic solution by controlling the electric quantity in the electrolysis and subsequent decomposing the solution, Al(OH)3 could yield with very large rate and high efficiency. The experiments also indicate that the quality of aluminum hydroxide product is greatly affected by the impurity silicon.

Kinetics of crystal growth on seeded precipitation of sodium aluminate solutions with new device

A new device was designed,which can effectively avoid the undesired nucleation and agglomeration of fine particles on the experimental results during the sead ed precipitation of sodium aluminate solution,and moreover,the experimental co nditions are nearly kept constant during the experiment. With the new device,it is proven that a good result can be obtained on the kinetics study of the cryst al growth in seeded precipitation of sodium aluminate solution.Experiments were carried out with the concentration of Na2O （Nk）170 g/L,the mole ratio of Na2O to Al2O3 （αk） all between 1.52 to 2.01,at 65,70,75 ℃,respectively. And the kinetics equation of crystal growth of gibbsite was deduc ed.

Combined effect of amino and carboxyl group in α-alanine on seeded precipitation of sodium aluminate solution

α-alanine was adopted as a new additive to elucidate the seeded precipitation mechanism of sodium aluminate solution. α-alanine has the inhibitory effect at the initial period of reaction, but the favorable effect in subsequent reaction. The combined effect of amino and carboxyl group in α-alanine was confirmed by investigating the effect of propionic acid, ethamine and the mixture of propionic acid and ethamine (mole ratio 1-1) on the precipitation of sodium aluminate solution, respectively. The inhibitory effect derives from the adsorption of amino or carboxyl group in α-alanine on the active surface sites of gibbsite, which was confirmed by the alleviating inhibitory effects of propionic acid, ethamine and α-alanine due to the double crystal seed mass. The semi-quantitative IR spectrum analysis of the relative concentrations of Al2O(OH)62- with the band at about 550 cm-1 and polynuclear aluminate ion with the bands at about 880 cm-1 and 635 cm-1, indicates that the dynamic balance among some aluminate species present in sodium aluminate solution is broken due to the addition of α-alanine, thus resulting in the change of the seeded precipitation ratio of sodium aluminate solution.

Behavior of calcium oxalate in sodium aluminate solutions

The stability of calcium oxalate is critical for the removal of sodium oxalate from sodium aluminate solutions.This studyinvestigated the behavior of calcium oxalate in sodium aluminate solution containing sodium carbonate.Results show that calciumoxalate can be converted to tricalcium aluminate hydrate(TCA)and calcium carbonate in sodium aluminate solution and sodiumcarbonate solution,respectively.Elevating temperature,extending residence time,or increasing caustic soda concentration enhancesthe conversion ratio of calcium oxalate in sodium aluminate solution;as a consequence,anti-causticisation occurs.Stability ofcalcium-containing compounds in sodium aluminate solution containing sodium carbonate differs from that in sodium aluminatesolution or sodium carbonate solution.Na2CO3in aluminate solution accelerates the transformation of calcium oxalate;thus,aluminais lost because of4CaO·Al2O3·CO2·11H2O and TCA formation.Calcium carbonate,4CaO·Al2O3·CO2·11H2O and calcium oxalatecan change into TCA in sodium aluminate solution at elevated temperature.Calcium oxalate remains relatively stable in dilutealuminate solution within a short residence time at low temperature.Thus,a novel process for removal of sodium oxalate by limecausticisation was presented and employed in an alumina refinery in China.

Variation of soda content in fine alumina trihydrate by seeded precipitation

High soda content in fine alumina trihydrate（ATH） limits its application and increases the soda consumption. The variation of soda content in the fine ATH by seeded precipitation was determined by detection of electric conductivity of solution, soda content in ATH, measurement of particle size distribution and microscopic analysis. The results show that high concentration of sodium aluminate solution, ground circulative seed, low temperature or fast initial precipitation rate increases the soda content in ATH. Soda mainly exists in lattice soda and less soda in desilication product （DSP） exists in the fine ATH precipitated from sodium aluminate solution with concentration of Al2O3 （ρAl2O3） more than 160 g/L and mass ratio of alumina to silica （μSiO2） of 400, and lattice soda decreases with increasing initial precipitation temperature, aging seed, and low precipitation rate and precipitation time. Results also imply that -＋ 4）Na Al（OH ion-pair influences lattice soda content in ATH on the basis of electric conductivity variation.

晶种粒度对过饱和铝酸钠溶液分解结晶反应动力学过程的影响

以过饱和铝酸钠溶液为研究体系,以氢氧化铝为诱导分解结晶反应晶种,研究分析反应过程中晶种粒度对表观活化能的影响。结果表明,随着晶种粒度减小,表观活化能降低,分解率升高。晶种颗粒形貌近似于椭球形模型,基于该模型引入了比表面能对Arrhenius公式中的表观活化能进行修正,表观活化能与晶种粒度的倒数之间呈线性关系。这一结果表明,降低诱导结晶的晶种粒度使分解率升高的机理是由于晶种引入了额外比表面能,该比表面能降低了铝酸钠溶液分解反应过程的表观活化能,从而使分解率升高。建立了晶种粒度与反应分解率之间的定量关系,为过饱和铝酸钠溶液分解过程的优化控制提供了理论依据。

拜耳法铝酸钠溶液分解动力学

讨论了温度和晶种粒度对铝酸钠溶液分解过程中晶体生长的影响，认为添加的晶种粒度对分解速率有很大的影响；晶种的粒度大时其比表面积小，分解速度慢；晶种粒度小时其比表面积大，分解速度快。根据Ｍｉｓｒａ提出的动力学方程求出了该分解条件下的活化能，并将晶种瞬时质量因子引入动力学方程，求得的不同温度下分解速率常数能较好地符合阿仑尼乌斯公式。在分解过程中晶种的瞬时比表面积变化很小，可以忽略瞬时比表面积变化的影响。

强化铝酸钠溶液晶种分解过程的研究

用醋酸、磷酸等酸类对工业晶种进行处理得到的活性晶种 ,并通过分解试验检验了晶种的活性 ,对活性晶种的作用机理也进行了初步探讨。

非离子型表面活性剂对铝酸钠溶液晶种分解的影响

采用对比实验法研究非离子型表面活性剂对铝酸钠溶液晶种分解率及其产品粒度和形貌的影响。结果表明：添加某非离子型表面活性剂,用量在100～150mg/L范围内,可提高分解率6%左右;粒度分析及电子显微镜形貌观察表明非离子型表面活性剂可促进Al（OH）3晶体的附聚和抑制二次成核,产品平均粒径可提高16μm。对表面活性剂强化铝酸钠溶液晶种分解的机理研究表明,表面活性剂改变Al（OH）3颗粒的表面Zeta电位,同时使铝酸钠溶液的表面张力降低了20～30mN/m,从而可大幅度降低铝酸钠溶液的稳定性,加快晶体生长速度。非离子型表面活性剂能有效强化铝酸钠溶液晶种分解过程。

铝酸钠溶液碳化制备活化氧化铝

考察了铝酸钠溶液碳化法制备活性氧化铝的实验条件。结果表明不同的加料方式、沉淀时ｐＨ值和温度均对产物的物性结构有极大的影响。合适实验条件下，等ｐＨ值加料、变ｐＨ值加料和交替变ｐＨ值加料三种方式都可获得拟薄水铝石沉淀，在一定范围内可通过调节操作参数来控制拟薄水铝石的其它物化性质，如比表面、堆积密度等。拟薄水铝石再经高温加热脱水后生成所需的活性氧化铝。与通常采用工业氢氧化铝酸溶后用碱再沉淀的制备路线相比，本方法制备工艺简单且成本低。

铝酸钠溶液分解过程的理论及技术研究进展

铝酸钠溶液分解是碱法生产氧化铝过程的关键环节。总结铝酸钠溶液分解过程的理论及技术研究进展,论述铝酸钠溶液分解过程的热力学和宏观动力学、铝酸钠溶液的结构及其演变规律、氢氧化铝颗粒行为、分解体系固-液界面作用调控以及铝酸钠溶液分解技术等。认为铝酸钠溶液分解过程中有利于氢氧化铝析出的含铝离子是Al(OH)-4,调控溶液中其他复杂含铝离子结构向该类结构转变则有利于氢氧化铝析出;增大分解末期体系中最小颗粒尺寸是提高分解深度的关键;协同调控分解过程中溶液物理化学性质、离子结构和固-液界面作用的原理和方法是强化铝酸钠溶液分解技术研究的基础。

从铝酸钠溶液中析出一水软铝石的实验研究

通过热力学分析确定了铝酸钠溶液体系中三水铝石、一水软铝石平衡固相与温度和苛性比之间的关系。以三水铝石为前驱体,通过水热法处理,制得结晶良好、纯度较高的一水软铝石;升高温度,延长反应时间,减小前驱体粒度以及加入适量苛性碱都有利于三水铝石向一水软铝石的转变。以一水软铝石为晶种分解铝酸钠溶液的实验结果表明:分解原液浓度升高,分解率降低;晶种粒度减小,分解时间延长,分解率升高;在95℃,铝酸钠溶液只析出一水软铝石,且最大分解率可达43.19%;而在85℃以下,分解产物为三水铝石。实验结果与理论分析结果相吻合。

NaOH-NaAl(OH)_4-Na_2CO_3-H_2O体系活度因子的计算模型

应用Bromley模型,通过对氢氧化钠、铝酸钠和碳酸钠等溶液体系活度因子的实验数据进行校验与回归分析,获得了各电解质合理的Bromley参数,建立基于Bromley模型的NaOH-NaAl(OH)4-Na2CO3-H2O体系活度因子的计算模型,其适用范围为:质量摩尔浓度分别为m(NaOH)≤8mol/kg,m(NaAl(OH)4)≤3mol/kg,m(Na2CO3)≤3mol/kg且离子强度I≤9mol/kg。使用该模型和Rard方法计算所得水的活度比较结果表明:该模型正确有效,计算精度较高,各电解质的Bromley参数取值合理;该模型也可用于NaOH-NaAl(OH)4-H2O体系活度因子的计算。