CAREER EPISODE 1

Development of a Solubility/Super-Solubility Isotherm for Crystallizer Design.

CE1.1 Introduction

The above research was carried out between February and October 2013 (8 months), as part of my

Ph.D studies at the School of Chemical Engineering, University of Queensland, Australia. I was the

principal researcher with Dr. Karen Steel as the chief advisor, and Professor Edward White and Dr.

Stephan Tait as the co-advisors. The project was sponsored by Fluorsid S.p.a. Italy, in conjunction

with the Australian Research Council.

CE1.2 Background

1.2.1 The objective of the project

The aim of the project was to develop an industrial crystallization process, for the recovery of

fluoride values of spent pot lining, in the form of aluminium hydroxyfluoride hydrate

(AlF2OH.H2O). This is proposed as an intermediate product to be fed into the current Aluminium

trifluoride-AlF3 production process. The recycling process has become necessary as the cost of virgin

materials are surging, and there are enormous stock piles of spent pot lining globally, with a

continuous addition from the expanding aluminium industry.

1.2.2 The nature of the overall project

Spent pot-lining (SPL) is the used/discarded carbon cathode-linings from the electrolytic cells (or

pots) of an aluminium smelting plant. It is classified as a hazardous waste and its disposal in landfills

is prohibited by most governments. About 7-30 kg of spent pot lining is generated per tonne of

primary aluminium produced and this amount to a global output of about 1 million tonnes per annum

and is projected to increase by 6% per year by 2016. This is hazardous mainly due to its leachable
fluoride and cyanide content. The carbon lining is discarded when its integrity is compromised, and

this usually occurs between 3-8 years from the time of installing a new lining.

1.2.3 My work area

My particular work area was to define the solubility limits of this compound in a likely acidic

industrial solution; and this had not yet been done at the time of embarking on this project. The

success of any crystallization design process depends on the accuracy of the solubility data used.

Hence, this work was critical to the success of the design of a suitable industrial crystallizer. The

proposed recycling process involved the chemical leaching of ground spent pot lining with sulphuric

acid, and the crystallization of its fluoride content by partial neutralization using caustic sodium

hydroxide (NaOH).

1.2.4 A chart of the organisational structure

Figure 1.1 is the organisational structure of the spent pot lining recycling, research group.

Fluorsid/Australian
Research Council

(Project owner)

Principal
Advisor

Co-advisor 1 Co-advisor 2

Principal
Researcher
(Ubong Ntuk)

Fig. 1: Spent pot lining recycling research group, organisational structure.

CE1.3 Personal Engineering Activity

1.3.1 The tasks I undertook

To successfully achieve the research project objectives within the given time frame, I developed and

implemented a comprehensive research strategy. I started by using model compounds to obtain the

necessary thermodynamic data. The data was applied to industrial solutions to study variable

interaction, before optimizing the key controlling factors based on the outcome. The steps in my plan

were broken down as thus:

a. Isolate high purity aluminium hydroxyfluoride compound from pure laboratory reagents.

b. Equilibrate the pure compounds in model solutions of similar ionic strength as the industrial

leachate solutions.

c. Define the optimum conditions for a single phase crystallization.

d. Study the effect and interaction of common and non-common ions, temperature, chemical

potential and induction time on solubility.

e. Using ‘a’ to‘d’ above, I obtained a reliable solubility isotherm useful for the crystallizer design.

A comprehensive review of research scientific literature was carried on the optimum conditions for

synthesizing aluminium hydroxyfluoride. As observed in previous studies, very complex methods

and sometimes hazardous precursors for this synthesis were utilized. For example, in one of the

methods, hydrofluoric acid and ammonia were used as the source of fluoride and hydroxyl

respectively. The reaction was represented as Equation 1. In another method, aluminium

hydroxyfluoride was obtained by the reaction of an aqueous solution of aluminium chloride with

calcium fluoride in its particulate form. The resulting solution contained aluminium chlorofluoride

and calcium chloride (Equation 2). An aluminium oxy-compound was then added and the resulting

solution was heated to a temperature between 40 and 90oC to precipitate Aluminium hydroxyfluoride

(Equation 3).
6NH4OH + Al2(SO4)3 + xAlF3→ 3(NH4)2SO4 + Al2+xF3x (OH)6 (1)

(x is between 1- 2)

AlCl3 + CaF2 → AlF2Cl + CaCl2 (2)

3AlF2Cl + Al(OH)3 → 3AlF2OH + AlCl3 (3)

1.3.2 Strategies devised by me

After understanding the chemistry of the reactions, I tested the use of less hazardous precursor

materials and confirmed that sodium fluoride (NaF) and gibbsite (Al(OH)3) could be used as the

source of fluoride and aluminium respectively, while sulphuric acid (H2SO4) was used for digestion

and caustic sodium hydroxide (NaOH) was used to supply hydroxyls for the crystallization reaction.

I successfully synthesised the very same phase of the aluminium hydroxyfluoride compound using a

very simple procedure. I identified the final product with standard techniques, x-ray powder

diffraction (XRD), nuclear magnetic resonance (NMR) and infrared spectroscopy (IR). Elemental

analysis using the alkali fusion method showed that the purity was over 95% and that was

satisfactory for the purpose.

I conducted the solubility studies by equilibrating excess of the aluminium hydroxyfluoride dry

powder in pure (de-ionised) water and acidic solutions of varying concentration of 2, 4, 6, 8 and 10

wt % H2SO4. Tests at each acid concentration were conducted in triplicates. The mixtures were

stirred at 300 rpm in sealed bottles and maintained at constant temperature (± 1oC) in a water bath.

Regular pH checks indicated an equilibration time of approximately 15 days. At this point, I took

samples of the supernatant via a filter syringe for analysis. The filtered solutions were analysed for
total concentrations of aluminium (Al), sodium (Na), and sulphur (S) using inductively coupled

plasma membrane atomic emission spectroscopy technique (ICP-AES).

1.3.3 How I applied my engineering knowledge and skill

Using the knowledge of chemical thermodynamics and speciation modelling with PhreeqC (a

speciation software), I derived the solubility product constant for the system at varying temperatures.

The negative log of the solubility constant (pKsp) at 25oC was obtained as 24.52 ( 0.05) and was

found to vary linearly with temperature; hence, the Van’t Hoff principle represented by Equation 1.1,

was used to obtain the thermodynamic properties of the system. The enthalpy and entropy of

dissolution were obtained as -23.5 ( 2.9) kJ/mol and 547 (± 10%) J/K respectively.

ln 𝐾𝑠𝑝 = −∆𝐻⁄𝑅𝑇 + ∆𝑆⁄𝑅 (1.1)

Where 𝐾𝑠𝑝 = Solubility constant

∆𝐻 = Enthalpy (change) of dissolution (kJ/mol), 𝑅 = Universal gas constant (8.314 J/mol.K)

𝑅 = Absolute temperature (K), ∆𝑆 = Entropy change of dissolution (J/K)

Having obtained the necessary thermodynamic data, the solubility isotherms were developed as

shown on Figure 1.2. This was tested experimentally with industrial solutions and found to be an

acceptable model of the system. From the results obtained, aluminium hydroxyfluoride was found to

be insoluble in water, but soluble in acidic solutions with a magnitude dependent on the temperature

and pH of the solution. It was also found that common and non-common ions had negligible effect

on the equilibrium of the system. This made it possible to adopt the obtained Isotherm in designing

the industrial crystallizer for the recycling of spent pot lining.

1.3.4 Creative design/original work

The developed solubility isotherm was the most useful tool in designing a suitable crystallizer for

this system. It was applied in predicting and maximizing product recoveries. For example, a feed

solution at pH 2.5 and at a temperature of 25oC will contain about 1mol (AHF)/kg (sol). To obtain

up to 99% recovery of the product, the pH could be increased to 5.0 thereby reducing the solubility

to about 0.003mol/kg. Similarly about 94% recovery could be obtained by increasing the temperature

of from 25oC to 90oC. This makes it possible to control the product yield and quality by manipulating

the crystallization conditions.

1
AHF solubility (mol/kg acid solution)

0.1

0.01

Expon. (25C)
Expon. (30C)
0.001
Expon. (50C)
Expon. (70C)
Expon. (90C)

0.0001
1 2 3 4 5
pH

Figure 1.2: Solubility Isotherm of aluminium hydroxyfluoride hydrate.

1.3.5 Technical difficulties / Team work

The major difficulty I encountered was that it took much longer than expected for a pure solution to

attain equilibrium. I found that this was due to the bonding orientation in the crystal lattice. To

circumvent this problem, I used a crystallization route at elevated temperatures, to attain equilibrium.

This resulted in a two-fold increase in the speed of reaction as the dissolution process is exothermic

in nature. In the course of doing this research, I had to constantly consult with my advisors. I also

had to regularly keep to the terms of reference and the goals of the project. As the primary

researcher, sometimes the opinions of my supervisors contradicted one another. At such times, I

arranged for a face-to-face general meeting to sort out the differences, and this always solved the

issues.

CE1.4 Summary

All the terms of reference of this project were met satisfactorily and within a timely manner. Due to

the success of this work, a bench scale pilot plant is underway after the successful implementation at

laboratory scale. Making such a significant contribution to a project of this scale provided me great

satisfaction in my career.