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Minimization of scaling and corresponding buffering capacities of these

residual alkalis in bauxite refinery residues implications in land


reclamation programs


Name: Suseendaran Babu
Student no: n8723095
Supervisor: Dr. Sara Couperthwaite
Professor Graeme Millar
Keywords: Bauxite residue, scaling, sodalite,
Land remediation, residual alkali
Due date: 25/10/2013
Department: Chemistry, Physics and Mechanical Engineering
Subject: ENN 590 Project Report





Table of Contents
1. Research problem
1.1. Rationale for investigation

2. Literature review
2.1.Bayer Process
2.2.Red Mud
2.3.Sodalite and Cancrinite
2.4. DSP scaling
2.5.Neutralised Red Mud
2.6.Red Mud in Land Remediation

3.Methodology
3.1.Synthesis of Sodalite
3.2.Synthesis of Hydrotalcite
3.3.Acid Digestion.

4. Characterisation

4.1. X-ray diffraction
4.2.Infrared spectroscopy
4.3.Analysis of XRD pattern of sodalite prepared under different conditions
4.3.1.XRD pattern analysis of unwashed sodalite prepared different temperatures
4.3.2.XRD pattern analysis of sodalite prepared under different temperatures
4.3.3.Analysis of IR pattern of sodalite
4.3.4.Analysis of IR pattern of sodalite prepared under different conditions
4.3.5.Analysis of IR pattern of sodalite prepared under different temperatures
4.4.Analysis of XRD pattern of Hydrotalcite prepared under different conditions
4.4.1.Analysis of IR pattern of Hydrotalcite prepared under different conditions



5.Acid stability of Sodalite and Hydrotalcite
5.1.Scale formation
5.2.Land remediation
6.Optimisation of Alumina Digester design
7.Conclusion
8.References
















List of tables:
1.sodalite synthesis using different liquor.
2.preparation of Sodalite at different temperatures.
3.Hydrotalcite Sample preparation observations.
4.Acid digestion Experimental observations.
5.Difference between Tube and Autoclave Digesters.
6.HT_6g/l 10 pH.
7. HT_5g/l 10 pH.
8. HT_4g/l 10 pH.
9. HT_3g/l 12 pH.
10. HT_3g/l 11 pH.
11. HT_3g/l 10 pH.
12.Syn_130 KP.
13. Syn_180 KP.
14. Syn_170 KP.
15. Syn_160 KP.
16. Syn_150 KP.
17. Syn_140 KP.





List of Figures:
1.Bayer process schematic diagram.
2.Sodalite Cage structure.
3.Cancrinite Cage structure with linear channels.
4. XRD pattern of sodalite prepared under different conditions.
5.XRD pattern of unwashed sodalite prepared under different conditions.
6.XRD pattern of sodalite prepared under different temperatures.
7. IR pattern of Sodalite and starting material.
8.IR pattern of sodalite prepared under different conditions.
9.IR pattern of sodalite prepared under different temperatures.
10.XRD pattern of Hydrotalcite prepared under different conditions.
11.IR pattern of Hydrotalcite and starting materials.
12.IR pattern of Hydrotalcite prepared under different conditions.
13.HCL acid digestion of sodalite prepared under different temperatures graph.
14.HCL acid digestion of Hydrotalcite prepared under different conditions graph.
15.Tube Digester
16.Autoclave Digester
17. A) Base column B) Agitated column C) Baffled column D) Base tank D) Baffled tank.
18. Slurry flow velocity vectors in digesters. A) Base column B) Agitated column10 rpm C) Agitated column - 52
rpm C) Agitated column - 80 rpm E) Baffled column.
19.RTD curves in digester.
20. Expanded view of RTD curve.
21.Inlet nozzle and steam injection nozzle.
22.RTD graph.
23.Flow region free turbulent flow.
24.Generic structure of Silane - containing polymer.
1.RESEARCH PROBLEM

This research addresses two areas in the alumina industry regarding by-products: 1) scaling and 2) waste
management and disposal.
1. The formation of aluminosilicate scale on heating tube surfaces has a significant impact on alumina
industry due to reduced production rates during plant shutdowns for cleaning and the costs associated
with cleaning operations. There is limited information available in literature about the effect of
temperature on the solubility of aluminosilicate structures in acidic conditions, which is the primary
method for removing scale in industry.
2. Apart from the formation of scale throughout the plant, the seawater neutralisation of bauxite refinery
residues results in the formation of mixed hydroxide mineral called Hydrotalcite. Both sodalite and
Hydrotalcite end up in large tailing dams along with the bauxite refinery residue. A number of
industries are investigating the beneficial use of bauxite refinery residue in land remediation programs,
however there is limited research on the stability of residual alkali in the residue (sodalite, Cancrinite,
lime and Hydrotalcite) when exposed to naturally occurring organic acids found in soils.

The overall aims of this project are to determine the conditions required to form the least stable sodalite scale
to minimize acid washing, suggest alternative digester designs to prevent sodalite scale forming and
approximate the life expectancy of alkali residues in mitigation of acidic soils
Specific aims:
1. Synthesise and characterise sodalite and Hydrotalcite using different parameters.
2. Assess the acid stability of sodalite and Hydrotalcite and estimate their environmental implications in
land remediation applications.
3. Investigate literature and determine the best digester design to minimise sodalite scaling on heat
exchange surfaces.


1.1.RATIONAL FOR INVESTI GATION

Red mud is a serious problem for mining industries both in an economical and ecological perspective. Since
the amount of red mud produced is over 120 million tons per year and with no viable remarketing options, its
application in land remediation and reclamation programs are of great research interest. Generally most of the
researches in this area are concentrated on reducing the alkalinity of red mud to optimum pH level to support
vegetation. But it is also equally important to have a deeper understanding of the consequences which will
occur due to reactions between neutralized red mud and vegetation reactions in land remediation process.

As a mechanical engineer it is essential that I have a broad knowledge in an array of sciences to ensure a
holistic approach to an industry problem can be made. This research will give me a deeper understanding of
the chemical structures, properties and reactions within the alumina industry, which will help me in
maintaining similar mining equipment and optimizing their design so that a more beneficial waste is
produced.

















2.LITERATURE REVIEW

Louis le Chatelier, a French mining engineer in 1855 created a technique to obtain alumina from bauxite by
sintering with sodium carbonate and leaching the sodium aluminate in water. Aluminium hydroxide was then
precipitated using carbon dioxide; however the alumina obtained in this technique was not pure. After the
development of the Hall-Heroult cell, the demand for pure alumina increased since it became the raw material
for aluminium production. In 1888, an Austrian chemist Carl Joseph Bayer developed an improved process for
the production of aluminium hydroxide from bauxite, and the process came to be known as the Bayer process.

2.1.BAYER PROCESS:
This is a process of producing pure alumina from bauxite ore. The aluminium bearing minerals in bauxite are
gibbsite Al(OH)
3
, Boehmite AlO(OH) and diaspora AlO(OH) are selectively extracted. This process has
four steps: 1) digestion, 2) clarification, 3) precipitation and 4) calcinations (Alcan), which is shown in
Figure 1. The process begins with the preparation of bauxite by blending it uniformly and grinding it. The
grinded bauxite is then mixed with a hot NaOH solution in digester vessel at well above atmospheric pressure
(Hanahan et al., 2004; Hind, Bhargava, & Grocott, 1999; Jones & Haynes, 2011; Palmer, Frost, & Nguyen,
2009). The reactions of aluminium compounds in the digester are described below:

Gibbsite converted to aluminate ions: Al (OH)
3
+ Na
+
+ OH
-
Al (OH)
-
4
+ Na
+
Boehmite and diaspore converted
To aluminate ions: AlO (OH)+ Na
+
+OH
-
+ H
2
O Al (OH)
-
4
+ Na
+



Figure 1 Bayer process schematic diagram

During the digestion stage, the bauxite slurry is mixed with hot caustic NaOH solution at high temperatures
and pressures. The exact parameter varies with the kind of ore used and is based on the mineralogical form of
aluminium. Gibbsite bauxite is generally digested at 275-300 F (135-150C), while Boehmite and diaspore
are digested at 400-475F (205-245C) and above 482F (250C), respectively, at higher pressure
conditions(Hond, Hiralal, & Rijkeboer, 2007). At this high temperature and pressure scaling normally occurs
in the form of desilicate products, which greatly affects the performance of digester vessel (Hond et al., 2007).

Some additional reactions convert impurities such as SiO
2
, P
2
O
5
and CO
2
to relatively insoluble compounds
such as sodalite and Cancrinite(institute) (formed by the reaction of kaolinite clay, NaOH and Na
2
CO
3
).
Insoluble bauxite impurities and those forms during the digestion process form the waste residue of the Bayer
process, which is known as bauxite refinery residue or more simply red mud due to its colour. This waste
residue is separated from the valuable sodium aluminate stream via the clarification stage of the process and is
sent for neutralization treatments before being disposed in tailing dams.(Barnes, Addai-Mensah, & Gerson,
1999a; P. Smith, 2009; Xu, Smith, Wingate, & De, 2010)

Once the aluminium in the bauxite ore has been converted to aluminate ions (Al(OH)
4
-
), gibbsite is re-
precipitated using controlled parameters to ensure the aluminium hydrate precipitated from the digestion
liquor is of adequate size. The process is essentially the reverse of the digestion stage:
Al (OH)
4
-
+ Na
+
Al (OH)
3
+ Na
+
+ OH
-



Gibbsite hydrate is finally calcined to form alumina for the aluminium smelting process(institute):
2Al (OH)
3
Al
2
O
3
+ 3H
2
O

2.2.RED MUD:
Red mud is separated from the concentrated sodium aluminate stream, as it passes into the thickener tanks
during the clarification stage. Here solid impurities sink to the bottom as a fine settlement of particles. The red
mud is then washed thoroughly to recover caustic soda (used again in the digestion process) before being sent
to neutralizing plants or tailing dams(limited).

The composition of red mud is a mixture of compounds originally present in the bauxite ore and compounds
introduced during the Bayer cycle. Red mud commonly consists of iron, silica and titanium oxides. The pH of
red mud is generally >13 with strong ionic strength. Some of the important constituents of red mud are
sodalite, alumino-goethite, hematite (iron oxide), silica crystalline and amorphous, tricalcium aluminate,
Boehmite, titanium dioxide, muscovite, calcium carbonate, gibbsite and kaolinite. Trace quantities of metals
like arsenic, manganese, cadmium, chromium, nickel, mercury, beryllium and lead are also found(committee).
The alkali nature of bauxite residue is an important issue to consider and is mainly due to desilicate products
(DSP) and residual NaOH trapped in desilicate products or not removed during the washing stage.

The average amount of red mud produced ranges between 1.1-6.2 tons per ton of alumina produced,
depending on the original bauxite ore composition used (Johnston, Clark, McMahon, & Ward, 2010). Large
areas of land are cleared and developed into dams for storing bauxite residue. The sheer size of these dams
can be in the 10s of millions of tons, with the largest dam in the world (QAL at Gladstone, Queensland,
Australia) being visible from space. The waste residue can cause harmful effects to the environment by
affecting the vegetation, water bodies during extensive rain periods and minimally through air exposure.
Therefore, the sheer volume and potential environmental threat that red mud has on surrounding ecosystems
and communities is of major ecological and economic concern.

2.3.SODALITE AND CANCRANITE (DSP):

High temperatures and caustic solutions create a perfect environment for numerous residual alkali species to
form (predominately DE silicate products). Silica is present in bauxite ore in the form of kaolinite
(Al
2
Si
2
O
5
(OH)
4
) and quartz (SiO
2
). These silica compounds in the presence of concentrated NaOH and
alumina ions at high temperature in the digestion process tend to form sodium aluminosilicate crystals
(Sodalite (SOD Figure 2) and Cancrinite (CAN Figure 3)). The majority of these compounds are removed
after digestion and cooling of the liquor with the undigested red mud during the thickener stage. However,
DSP scaling does occur on pipes and vessels exposed to heat (Barnes et al., 1999a; Barnes, Addai-Mensah, &
Gerson, 1999b; Xu et al., 2010). The general formula of sodium aluminosilicate crystals are Na
6
[Al
6
Si
6
O
24
].
NaX where X represents CO
3
2-
, SO
4
2-
, 2OH
-
, 2Cl
-
anions in the cages of the structure, which is dependent on
the type impurities in the Bayer liquor(Barnes et al., 1999a; P. Smith, 2009; Xu et al., 2010). The crystal
structure of SOD is cubic and CAN is hexagonal. SOD has stacking of 14-hedra consisting of eight 6
membered rings, whereas CAN has the stacking of 11-hedra of 5 six membered rings and 6 four membered
rings. This arrangement helps Cancrinite in replacing Na
2
X with other compounds(Xu et al., 2010). The
reaction of lime (CaO), aluminate and silica in the digestion process also results in the formation of the
hydrogranet series (Ca
3
Al
2
(SiO
4
)
n
(OH)
12-4n
) of minerals : n=0 tri calcium aluminate, n=1 katoite, n=2
hibbschite and n=3 grossular (P. Smith, 2009). The large amount of hydroxyl groups associated with this
group of minerals also constitutes as residual alkali in bauxite refinery residues.


Figure 2 Sodalite Cage structure Figure 3 Cancrinite Cage structure with linear channels


2.4.DSP Scaling
Scaling is generally formed by sodium aluminosilicate crystals called sodalite
(3[Na
2
O.Al
2
O
3
.2SiO
2
.2H
2
O].Na
2
CO
3
). This scaling occurs at higher temperatures when the solution becomes
super saturated with respect to sodalite and sodium aluminosilicate, which react to form sodalite scaling on the
vessel walls. Removing scale from interior pipes and vessels is an excessive time and money consuming
process, even sometimes in case of extreme scaling the plant has to be shut down temporarily. To remove
scaling they use concentrated acids and specific reagents depending on the composition of the scale.
Sometimes during extreme scaling they remove it manually with jack-hammers (Fortin & Breault, 2004).

2.5.NEUTRALISED RED MUD:
To reduce the harmful effects of red mud many methods have been used to neutralize the residue, for example
infiltration of rain water and atmospheric CO
2
, acidic leaching, addition of gypsum and the seawater
neutralization method(Hanahan et al., 2004).

The seawater neutralization method is one of the most widely used methods to reduce the alkalinity of red
mud. In this technique the red mud is slurried with seawater and pumped at a controlled density towards the
red mud dam where chemical reactions take place. It helps to improve settling rates at the pond due to
agglomeration and reduces the alkalinity of red mud through the precipitation of hydroxycarbonate minerals.
The neutralizing capacity of seawater, compared to acid neutralization, on red mud has increased
considerably, due to the carbonate uptake during the precipitation of Hydrotalcite like compounds(Hanahan et
al., 2004). The seawater neutralization of red mud transforms free alkali to Hydrotalcite
(Mg
6
Al
2
(OH)
16
CO
3
.4H
2
O) and hydrocalumite ([Ca
2
Al(OH)
6
]
2
CO
3
.2H
2
O) both of which form slightly
different species depending on the synthesis conditions(Hanahan et al., 2004; D. McConchie, Clark, Hanahan,
& Fawkes, 1999; D. McConchie, Saenger, & Fawkes, 1996; David McConchie, Clark, Davies-McConchie, &
Ryffel, 2004; Palmer et al., 2009; H. D. Smith & Parkinson, 2005).

In summary, there are numerous forms of residual alkali in bauxite refinery residues. Those that will be
investigated in this research include sodalite, Cancrinite, Hydrotalcite, hydrocalumite and residual lime.


2.6.RED MUD IN LAND REMEDIATION:
Applications of Red mud include being used in the ceramic industry as an additive, as a raw material in the
cement industry, in the production of TiO
2
by leaching, in the building material industry and in land
remediation. Due to the sheer quantity of red mud that is produced annually (120 million tons)(Oeberg &
Steinlechner, 1996), the application of red mud in land remediation and reclamation programs have received
considerable interest in recent years.

Land remediation is a most promising application due to the reclamation of land and the volume of residue
that can be utilized. In most land remediation cases, the pH of red mud is reduced through the addition of
gypsum (CaSO
4
.2H
2
O), however selective grasses have been able to grow on untreated red mud. One of the
most important properties of soil is its pH, because soil pH dictates the type of vegetation that is able to be
sustained, however as a general rule a pH of 5.5 to 7.5 is suitable for the majority of vegetation(Bleam, 2012;
Sparks, 2003). The major impact of pH extremes on plant growth is related to the availability of plant
nutrients and soil concentration of plant toxic elements. In strongly acidic soils (pH <5.5), manganese and
aluminium can concentrate to levels that are toxic to plants and pose potential run-off risk with fish kills,
while at high pH the availability of nutrients such as phosphorous, iron, copper, zinc, boron and manganese
decreases(Bleam, 2012). Therefore, it is essential that the right soil pH is maintained to ensure plants have
access to all the nutrients that they need for growth and development. Plants take up these nutrients in the
form of ions and generally take up more cations than anions. So in order to maintain neutrality in the roots,
they release H
+
ions in the form of organic acids such as acetic, humic, oxalic, citric and tannic acid(Bleam,
2012).

Therefore, this investigation will focus on the stability of residual alkali commonly formed in bauxite refinery
residues when exposed to acetic, oxalic and citric acid environments. An assessment will be made on the
stability of the different residual alkalis (different mineral groups and the effect of digestion parameters on
DSP formation), potential detrimental effects on plant nutrition and growth, as well its potential in mitigating
acidic soil formation.



3.METHODOLOGY

The following section outlines the major milestones of the research project.

Phase 1: Preparation of materials
3.1.Synthesis of Sodalite
Effect of synthesis conditions on the stability of sodalite in a pressure reactor
Alumina concentration (amount of sodium aluminate)
Silica concentration (amount of Kaolin)
Alumina source (synthetic, mixture, real Bayer liquor)
Temperature (130, 140, 150, 160, 170, 180, 220C)

The following sodalite experiments are based on description reported by Jamialahmadi and Muller-
Steinhagen: Aluminium monohydrate forms of bauxite ore require relatively mild digestion temperatures and
caustic concentrations. These are typically of the order of 145
o
C and 4-5 M NaOH, respectively, compared to
170-265
o
C and up to 7M for ores containing the aluminium oxyhydroxide forms(H.muller, 1998),

Sodalite was prepared in this investigation by the digestion of pure Kaolin KW65 at 150
o
C for 30 minutes
(reactor time starts when the temperature reaches the desired value) in a high-pressure reactor using different
Bayer liquor compositions containing sodium aluminate (NaAl(OH)
4
)
,
sodium carbonate (Na
2
CO
3
)

and
sodium hydroxide (NaOH). There were 2 types of mixing conditions used to prepare Bayer liquor: 1) prior
mixing involved all components to be dissolved before being placed in the digester, and 2) in-situ mixing
involved all solid components of Bayer liquor to be placed in the digester before the addition of water. In a
number of tests a real Bayer liquor solution was used instead of water. The amount of kaolin added to the
100mL of Bayer liquor (synthetic or real) was either 1 or 2g for all tests requiring temperatures of 180C and
below. To synthesize sodalite at 220
o
C, 200 mL of liquor was required. This was because if we have 100mL
then due to the low volume of liquor the heat supplied is converted to latent heat and the temperature will not
reach 220
o
C. The conditions to prepare each sodalite sample are provided in Table 1. After the required
digestion time the slurry was collected using a centrifuge set to 4000rpm for 10mins. The supernatant was
discarded and the solid washed 3 times with 200mL of water to remove any un-reacted starting materials. The
solid was dried for 48hours in an oven set to 90
o
C.
Table 1 Sodalite synthesis using different liquors
Type of liquor Temperature
(
o
C)
Time
(min)
NaAl(OH)
4
(g)
NaOH
(g)
Na
2
CO
3

(g)
Liquor volume
(mL)
Synthetic liquor 150 30 90 7.5 7.725 250
Real liquor 150 30 250
Mixed liquor 150 30 56.152 2.364 4.60 BL2:
125 ml of real liquor
+ 375 ml water.
250ml of dilute real
liquor mixed with
synthetic liquor.
Synthetic liquor
(prior mixing)
220 30 67.1 15 6.18 200
Real liquor 220 30 As above

Mixed liquor 220 30 56.152 2.3644 4.60 As above

The characterization of the 6-sodalite samples prepared using different liquors was required to determine that
sodalite formed and to assess the method that produced the most pure sample. The experimental conditions
that produced the most pure sample of sodalite would be used for all future sodalite experiments. After
looking at the characterization results, sodalite prepared from synthetic liquor at 150
o
C has been chosen for
further experiments.
Therefore, synthetic liquor that was mixed before entering the digester was used to study the effect of
temperature on the resultant sodalite structure. The temperatures investigated were 130, 140, 150, 160, 170
and 180C. First 1L of synthetic liquor was prepared with the following composition: NaAl(OH)
4
= 233.057 g,
NaOH = 75g and Na
2
CO
3
= 30.90. Details of the experiment are outlined in Table 2.





Table 2 Preparations of Sodalites at Different Temperatures
Different temperatures Sample ID and
temperature range
Comments
Sodalite prepared at 130
o
C Syn130_temp
165 130
o
C
100ml of liquor in reactor and add 1g of Kaolin.
Keep at desired temperature for 30 minutes.
Sodalite prepared at 140
o
C Syn140_temp
167 140
o
C
As above
Sodalite prepared at 150
o
C Syn150_temp
171 150
o
C
As above
Sodalite prepared at 160
o
C Syn160_temp
174 160
o
C
As above
Sodalite prepared at 170
o
C Syn170_temp
177 170
o
C
As above
Sodalite prepared at 180
o
C Syn180_temp
184 180
o
C
As above

3.2.Synthesis of Bayer Hydrotalcite
Alumina concentration
pH end point
Depending on the above-mentioned factors, Hydrotalcite has been synthesized. A prepared Bayer liquor
solution (2L) was place into the 60L bucket, situated below an overhead stirrer (set speed to 400 rpm). Then
using 2 peristaltic pumps and tubing with an internal diameter of 3.2mm were placed into two 10L seawater
drums and attach to the 60L bucket. The pump speed was set to 10mL/min and seawater was added until the
required pH of the neutralized solution was obtained. Throughout the process and for an additional 48 hours
the solution was continually stirred. After 48 hours of stirring the solution was filtered using a 5L Buchner
funnel and flask. The semi-dry precipitate was placed into a 10 L bucket containing 9L of DI water. This
washing stage was used to remove sodium chloride that formed along with Hydrotalcite. The vacuum filtering
process was repeated and the semi-dry filter cakes were placed into an oven to dry for 1 week. The solution
was disposed. This process was repeated until 10 grams of product was made. The precipitates were crushed
using an agate mortar and pestle, with a particle size of less than 125 micrometer. Details for each
Hydrotalcite synthesized are outlined in Table 3.


Table 3 Hydrotalcite sample preparation observations
Aluminum concentration
(g/L)
NaOH
(g)
Na
2
CO
3

(g)
Volume of SEL
(mL)
Volume of Bayer liquor
(mL)
Final
pH

3 58.98 6.34 63.42 2000 10.25
3 58.97 6.34 63.42 2000 11.00
3 58.99 6.36 64.00 2000 12.02
4 54.84 8.45 84.57 2000 10.70
5 50.69 10.56 105.71 2000 10.42
6 46.55 12.68 126.85 2000 10.47

3.3.Acid digestion

Initially, 0.25 g of sodalite/Hydrotalcite was weighed on an analytical balance and placed into a 100 mL
beaker. The actual masses of sodalite and Hydrotalcite tested are outlined in Table 4. A pH probe was then
calibrated with pH buffers 7 and 4. After this, 50 mL of DI water was added to the beaker using a 50 mL
pipette. The pH was then monitored until it had stabilized and recorded as the pH with 0mL of acid added. To
the 50mL of water containing sodalite/Hydrotalcite, 100 L of 0.5M hydrochloric acid (HCl) was added and
allowed to stir for 30 seconds before the pH and volume of acid added was recorded. This process was
repeated until all the sodalite/Hydrotalcite had dissolved or the pH stabilized below 2. (During the experiment
when the pH did not significantly drop after the addition of acid the increment of acid added increased to 250,
500 and 1000 L).




Table 4 Acid Digestion Experimental observations
Sample ID
Mass of sodalite/Hydrotalcite in
DI water (g/50mL)
Total acid volume used
(mL)
Final pH
Syn_130 KP 0.2516 12.15 1.58
Syn_140 KP 0.2514 14.75 1.27
Syn_150 KP 0.2521 15.00 1.26
Syn_160 KP 0.2514 14.35 1.16
Syn_170 KP 0.2530 15.60 1.13
Syn_180 KP 0.2527 14.95 1.18
HT_3g/L 10pH 0.2523 11.85 1.34
HT_3g/L 11pH 0.2544 12.08 1.29
HT_3g/L 10pH 0.2527 13.58 1.31
HT_4g/L 10pH 0.2563 12.58 1.26
HT_5g/L 10pH 0.2556 14.55 1.18
HT_6g/L10pH 0.2560 14.05 1.16














4.CHARACTERISATION TECHNIQUES
3.METHODOLOGY
4.1.X-Ray diffraction

X-Ray diffraction patterns were collected using a Philips Expert wide angle X-Ray diffractometer, operating in
step scan mode, with Co K radiation (1.7903 ). Patterns were collected in the range 5 to 90 2 with a step
size of 0.02 and a rate of 30s per step. Samples were prepared as Vaseline thin films on silica wafers, which
were then placed onto aluminium sample holders. The XRD patterns were matched with ICSD reference
patterns using the software package High Score Plus. The profile fitting option of the software uses a model
that employs twelve intrinsic parameters to describe the profile, the instrumental aberration and
wavelength dependent contributions to the profile.

4.2.Infrared spectroscopy

Infrared spectra were obtained using a Nicolet Nexus 870 Fourier Transform infrared spectrometer (FTIR)
with a smart endurance single bounce diamond ATR (attenuated total reflectance) cell. Spectra over the
4000-350 cm
-1
ranges were obtained by the co-addition of 64 scans with a resolution of 4 cm
-1
and a mirror
velocity of 0.6329 m/s.

4.3.Analysis of XRD patterns of sodalite samples formed under different condition:

The sodalite samples prepared under different conditions are compared with the initial materials used in
the preparation and pure sodalite reference sample (Figure 4).


Figure 4: XRD patterns of sodalite samples prepared under different conditions.


First on comparing the samples with Na
2
CO
3
- XRD pattern we found three samples were clearly showing
presence of sodium carbonate. The first sample Syn150
o
C_1g_insitu mixing matches the position of lines
and intensity ratio similar to sodium carbonate in the range of 35 to 45 2. The second sample
Mix220
o
C_2g_insitu mixing shows the presence of lines in the 35 to 45 2 with lesser intensity ratio
indicating that the percentage of sodium carbonate is smaller compared to the earlier sample. The third sample
Real220
o
C_2g_insitu mixing has similar lines in a smaller range of 35 to 42 2 with very low intensity
ratios. Syn150
o
C _2g_insitu mixing and Syn150
o
C_1g_prior mixing shows very little disturbance in the
pattern in the sodium carbonate range indicating very little of sodium carbonate is present in these samples.

Now let us compare the samples with sodium aluminate anhydrous, which is indicated predominantly by the
presence of twin peaks at around 25 2. The samples Syn150
o
C_1g_prior mixing, Syn150
o
C_2g_insitu
mixing, and Mix220
o
C_2g_insitu mixing all show the twin peak at around 25 2, indicating the presence
of sodium aluminate anhydrous in these samples. The intensity of this impurity is much higher in the insitu
mixing samples than in the Syn150C_1g_prior mixing sample, which is predominately sodalite. While the
samples Real220
o
C_2g_insitu mixing and Syn150
o
C_1g_insitu mixing did not show the characteristic
twin peak of sodium aluminate or any other typical aluminate peaks.

Kaolin KW65 has a slanting peak in the region of 23 to 30 2. Syn150
o
C _2g_insitu mixing has a
considerable amount of kaolin remaining in the sample shown by the slanting peak between 22 and 30 2.
The remaining samples have a minimal amount of Kaolin, which indicates the complete digestion of kaolin
during sodalite formation.

Finally let us compare the samples with the sodalite reference pattern. The XRD pattern confirms the
formation of a relatively pure sodalite structure for Syn150
o
C_1g_prior mixing. The sodalite reference
pattern has lines appearing at around 17, 27, 35, 40 and 43 2, which corresponds well with the sample
Syn150
o
C_1g_prior mixing. The sodalite sample prepared in this study has a different intensity ratio of the
XRD lines, which may be due to the difference in the sodalite structures. Sodalite has the ability to have a
number of different anions trapped in the many cage structures, and it is believed differences in these trapped
species are responsible for the intensity shifts. The sample prepared using real Bayer liquor has a more
complex XRD pattern than the other sodalite samples and starting materials, indicating additional phases may
have formed from the many impurities in the real liquor. It is also noted that prior mixing of the chemical
components formed a more pure sodalite product. Insitu mixing samples had many of the raw starting
materials still present, especially sodium aluminate and sodium carbonate.

Based on these results the continuing experiments followed the prior mixing method at 150C and an
aluminate concentration of 1g/L.
4.3.1.XRD pattern analysis of unwashed sodalite samples prepared under different temperatures:

All unwashed samples have a similar XRD pattern (Figure 5), especially in the region 35 to 40 2, with very
low intensity lines for sodalite being observed. The XRD pattern is dominated with the presence of undigested
starting material. The samples have a minimal amount of sodalite compared to starting materials sodium
carbonate/aluminate anhydrous. Therefore, additional washing is required to remove the starting materials
leaving the samples containing predominantly sodalite.

4.3.2.XRD pattern analysis of sodalite samples prepared at different temperatures:
After washing the samples, all sample XRD patterns show significant changes (Figure 6). All samples showed
lines at around 17, 27, 35, 40 and 43 2, which matches the reference sodalite pattern. Therefore, sodalite
was successfully formed at all digestion temperatures. A similar observation on the intensity ratio of the
synthesized samples and the reference pattern are noted. Again, this is thought to be due to differences in
starting material used (possibly the synthesized sodalite structure is based on a carbonate-sodalite, while the
reference pattern is based on a sodalite-chloride structure).


Figure 5: XRD patterns of unwashed sodalite samples prepared at different temperatures

Figure 6: XRD patterns of sodalite samples prepared at different temperatures.








4.3.3.Analysis of infrared spectra of sodalite:
The infrared spectra for the materials to prepare Bayer liquor and the most pure sodalite sample are provided in
Figure 7 to help in the interpretation of the results.

Figure 7: Infrared spectra of sodalite and starting materials.

Sodium carbonate (Na
2
CO
3
) has a characteristic strong intensity band located at around 1419 cm
-1
; this band
is very broad and associated with the stretching vibrational modes of carbonate (CO
3
2-
). It also has another
high intensity band located at around 850 cm
-1
; this band is much sharper and is assigned to the bending
modes of CO
3
2-
. Following these bands there are small intensity bands in the region 650 to 400 cm
-1
.

Sodium aluminate anhydrous (NaAlO
2
) has a high intensity bands at around 780, 600, 500 and 400 cm
-1
.
These bands are associated with the Al-O stretching and bending modes of sodium aluminate. The absence of
any bands above 3000 cm
-1
confirms that the starting material indeed did not have any associated water.

Kaolin (Al
2
O
7
Si
2
) has a medium intensity overlapping bands between 3700 and 3450 cm
-1
, which is the
characteristic OH stretching region. Its interesting to note that kaolin does not possess any OH groups, so it is
thought that it is contaminated slightly with kaolinite (Al
2
Si
2
O
5
(OH)
4
). XRD did not observe kaolinite in the
structure, possibly only a minor phase below the noise of the pattern, however in infrared spectroscopy is very
sensitive towards OH vibrational modes and thus was observed. Further down the spectrum, a wider band
with multiple high intensity bands between 980 and 880 cm
-1
are observed. These bands correspond with the
stretching vibrations of Si-O and Si-(OH)
2
modes. At around 780 and 720 cm
-1
two close bands with relatively
low intensity are also observed. At the lower wavenumber region, 3 bands with similar intensity are observed
between 450, 430, 420 cm
-1
and are associated with Al-O and Al-O-Si vibrational modes of kaolin.

Sodalite (Na
8
(Al
6
Si
6
O
24
)CO
3
) forms a very broad low intensity band ranging from 3600 to 2350 cm
-1
. This
band suggests that water, OH
-
and CO
3
2-
are present in the structure. A very small band with low intensity is
observed at around 1613 cm
-1
, which is typical of water bending modes, while the intense band at 1419 cm
-1
is
typical of carbonate modes similar to those in Na
2
CO
3
. At lower wavenumbers there are a number of broad
bands between 950 and 350 cm
-1
. Comparison of the starting materials shows that the sodalite spectrum is
comprised of a number of bands from sodium carbonate/aluminate and kaolin. The Si-O vibration modes are
observed at around 950 cm
-1
, while carbonate bands are observed at 850 cm
-1
and Al-O and Al-O-Si
vibrational modes appear below 850 cm
-1
.












4.3.4.Analysis IR spectra of sodalite prepared under different conditions:

The sodalite samples prepared using different Bayer liquor compositions and digester conditions are provided in
Figure 8.

Figure 8:Infrared spectra of sodalite samples prepared under different conditions.

Real220
o
C_2g_insitu mixing a very broad band starting at around 3600 cm
-1
, similar to the one observed in
the sodalite spectrum. At 1412 cm
-1
a very low intensity sharp curve is formed. In the region of 946 cm
-1

unlike the pure sodalite a small sharp curve is formed indicating the presence of Kaolin, followed by a high
intensity curve in the region of 850 cm
-1
confirming presence of carbonate. In the region of 590, 510 and 490
cm
-1
typical of aluminate bands is formed. This sample predominately has impurities and undigested starting
material compared to sodalite, also observed in the XRD pattern.

Real220
o
C_1g_insitu mixing also has a very broad low intensity band spanning about 1000 cm
-1
from 3600
cm
-1
. As in the previous sample at 1409 cm
-1
a very low intensity sharp curve is observed, corresponding to
carbonate anions in either Na
2
CO
3
or sodalite. In the region 980 (high intensity) to 880 cm
-1
(medium
intensity) is observed, which infers the presence of Si-O bonding environments. In the region of 780 and 720
cm
-1
, two bands are formed with earlier having lower intensity and the later one having higher intensity
indicating the presence of aluminate. There is a band formed in the region of 400 cm
-1
, which again
substantiates the presence of aluminate. Thus, the sample has impurities and undigested starting material, also
confirmed by the corresponding XRD pattern.

Mix220
o
C_2g_insitu mixing in the higher wavenumber region (3700 to 3450 cm
-1
) there are a multiple of
sharp overlapping bands similar to those observed in for Kaolin, indicating that it was not fully digested. A
band at 1410 cm
-1
, is indicative of carbonate and suggests this sample also contains this starting material as
well. Bands at 990 and 830 cm
-1
with higher and lower intensities respectively infer the presence of kaolin. In
the region of 710 and 650 cm
-1
a very small band is observed indicating the presence of sodalite is relatively
very minimal. Typical aluminate bands at 600, 500 and 400 cm
-1
with very low intensity are formed. In the
region 460, 430 and 400 cm
-1
kaolin bands are observed. This sample has high amounts of undigested Kaolin
with impurities and starting materials.

Syn150
o
C _2g_insitu mixing as in the previous sample, however to a lesser extent, there are some sharp
bands located in the high wavenumber region that indicate a small Kaolin contamination in the sample. The
presence of carbonate is indicated by the band at 1400 cm
-1
. In this sample the band intensities were generally
very low. In the region between 830 and 800 cm
-1
, small bands with low intensities are observed and may
indicate the presence of sodalite. In the region 500 cm
-1
, a broad band near 400 cm
-1
infers the presence of
Kaolin. Thus, this sample is dominated by starting materials.

Syn150
o
C _1g_insitu mixing a very broad band spanning across the 3000 cm
-1
region indicates the presence
of water, hydroxyl and carbonate species. In the region of 1408 cm
-1
a band with lower intensity is observed
confirming the presence of carbonate in the sample. In the region of 950 cm
-1
a small band is observed in a
similar way as the sodium aluminate spectrum, thus suggesting aluminate was not fully digested. Next to this
in the region of 875 to 830 cm
-1
contains two bands, one sharper and one broader, indicating the presence of
sodalite. Following this in the region between 600 and 400 cm
-1
more bands typical of the aluminate spectrum
are observed. Compared to other samples this sample has a higher amount of sodalite but still has a lot of
impurities.

Syn150
o
C_1g_prior mixing a very broad band spanning across the 3000 cm
-1
region indicates the presence of
water, hydroxyl and carbonate species. The absence of multiple sharp bands indicates a minimal
contamination from Kaolin. In the region 1415 cm
-1
a small broad curve with relatively lower intensity is
formed indicating the presence of carbonate(Rives V, 1993), but due to the low intensity indicates that it is not
predominately from Na
2
CO
3
. An asymmetric stretch of the Al-O-Si sodalite framework is observed at around
950 cm
-1
, while the symmetric stretch of the sodalite framework is observed at around 670, 630, 610 and 580
cm
-1
(K. Zheng, 1997). Compared to all the other samples this sodalite sample has minimal impurities
(undigested material). These results correspond well with the XRD patterns and confirm that this method of
synthesis is required for the temperature dependent experiments.

4.3.5.IR analysis of sodalite samples at different temperatures:

Infrared and XRD has confirmed that a sample prepared from prior mixing and preparation of the synthetic
Bayer liquor forms sodalite predominantly (Figure 9). Therefore, a number of sodalite samples were prepared
in the same manner but were digested at different temperatures (130, 140, 150, 160, 170, and 180C). Infrared
spectra and XRD patterns confirm the main phase that forms is sodalite, however slight changes in bonding
environments of these sodalite samples are observed in the infrared spectra.

Sodalite_180
o
C the water-bending band observed at 1613 cm
-1
is very similar in intensity and broadness to
the reference sample. The band at 3529 cm
-1
has shifted to higher wavenumbers and is no longer a relatively
sharp band. No changes in the band at 1419 cm
-1
are observed. The band observed at 946 cm
-1
is broader with
less intensity. The bands observed at 875 and 809 cm
-1
are lower in intensity and appear to be becoming more
broad when compared to Sodalite_150C. Bands at 686, 663, 612, 582 and 526 cm
-1
are very broad with low
intensity. The band at 409 is similarly sharp with less intensity.


Figure 9:Infrared spectra of sodalite samples prepared at different temperatures.

Sodalite_170
o
C the band observed at 1613 cm
-1
is much similar in intensity and broadness to the reference
sample. The band at 3529 cm
-1
is slightly shifted with higher intensity and sharpness. The band at 1419 cm
-1
is
slightly lesser in intensity and sharpness. The band observed at 946 cm
-1
is broader with less intensity. The
band forms at 875 cm
-1
is lesser in intensity and similarly sharp. The band observed at 809 is highly broad
with lower intensity. Bands in the region 686, 663, 612, 582 and 526 cm
-1
are very broad with lower intensity.
The band at 409 cm
-1
is similarly sharp with less intensity.


Sodalite_160
o
C the band observed at 1613 cm
-1
is much similar in intensity and broadness to the reference
sample. The band at 3529 cm
-1
is similar in all aspects. The and at 1419 cm
-1
is sharper with higher intensity.
The band observed at 946 cm
-1
is more broad with less intensity. The bands at 875 and 809 cm
-1
are sharper
with higher intensity. Bands in the region 686, 663, 612, 582 and 526 cm
-1
are comparatively closer than the
earlier sample to the reference but still it has lesser intensity and broad. The band at 409 cm
-1
has similar
sharpness with lesser intensity. Compared to earlier samples the intensity is high.

Sodalite_140
o
C the band at 1613 cm
-1
has slightly shifted before with higher intensity and more sharpness.
The band at 3529 cm
-1
is slightly shifted with higher intensity and sharpness. The band at 1419 cm
-1
is sharper
with higher intensity. The band at 875 and 809 cm
-1
are less intense and sharper. The bands in the region 686,
663, 612, 582 and 526 cm
-1
are more broad with high intensity with slight shift in their respective position.
The band 409 cm
-1
is broad with less intensity.

Sodalite_130
o
C the band at 1613 cm
-1
has very slightly shifted before with higher intensity and sharpness.
The band at 3519 cm
-1
is slightly shifted with higher intensity and sharpness. At 1419 cm
-1
the intensity is
lower with similar sharpness. At 946 cm
-1
there is a shift in band making it broad with lesser intensity. At 875
cm
-1
the band is sharper with higher intensity. At 809 cm
-1
the band is broad with lower intensity. Bands in the
region 686, 663, 612, 582 and 526 cm
-1
have slight shift with lesser intensity and more broadness. The band at
409 cm
-1
is broad with lesser intensity.

Overall, the spectra of the different sodalite samples appear to be very similar. The only notable change is an
increase in intensity of the band at 946 cm
-1
, which is characteristic to the Si-O stretching vibrations of the
sodalite framework. The sodalite structure is presumed to be a carbonate sodalite due to the intense bands at
1419 and the sharp band at 875 cm
-1
.




4.4.Analysis of XRD patterns of Hydrotalcite samples prepared under different conditions:

The Hydrotalcite samples prepared under different conditions are compared with reference patterns of
Hydrotalcite and starting materials (Figure 10)


Figure 10: XRD patterns of Hydrotalcite samples prepared at under different conditions.

The identification of aragonite (CaCO
3
) in the XRD patterns can be achieved by the doublet of peaks at 31
and 33 2. The sample Hydrotalcite_3g/L_pH10 observed bands at 31 and 33 2 with much lower
intensity but highest among the other samples indicating the presence of Aragonite. The samples
Hydrotalcite_3g/L_pH11 and Hydrotalcite_4g/L_pH10 had similar bands, however with a much lower
intensity compared to Hydrotalcite_3g/L_pH10 suggesting the presence of only minor amounts of aragonite
in the sample. The samples Hydrotalcite_3g/L_pH12, Hydrotalcite_5g/L_pH10 and
Hydrotalcite_6g/L_pH10 were not showing any significant noticeable changes the aragonite region, in their
respective XRD patterns, indicating if aragonite formed it is negligible.

Samples that contain calcite can be identified by the presence of a high intensity peak at 35 2. All the
samples had this high intensity suggesting that calcite was a major phase that formed during the seawater
neutralization reaction. The intensity of the bands slightly decreased as the final neutralization pH decreases
and when the aluminium concentration increased.

The Mg(OH)
2
reference pattern has a high intensity band at 22 2, followed by a relatively low intensity
bands at 45 and 59 2. The samples Hydrotalcite_3g/L_pH12, Hydrotalcite_3g/L_pH11 and
Hydrotalcite_3g/L_pH10 were observed to have bands in similar positions at 22, 45 and 59 2. The
samples Hydrotalcite_4g/L_pH10, Hydrotalcite_5g/L_pH10 and Hydrotalcite_6g/L_pH10 showed very
minimal amounts of magnesium hydroxide in the sample.

The formation of Hydrotalcite for all samples synthesized can be confirmed by the XRD patterns of the
samples. The reference pattern has a high intensity band observed at 14 2, followed by a series of low
intensity bands at 27, 42, 56 and 55 2. All the samples have bands observed in the region of 14, 27, 42, 56
and 55 2 confirming the presence of Hydrotalcite. A characteristic feature of the Hydrotalcite pattern is the
broadness of the peaks due to the poorly crystalline structure that forms. The intensity of the bands in all the
samples vary slightly. Of all the samples Hydrotalcite_3g/L_pH10 has the highest intensity followed by
Hydrotalcite_3g/L_pH10 and Hydrotalcite_3g/L_pH11.















4.4.1.Analysis of Infrared spectroscopy pattern of Hydrotalcite prepared under different conditions:

Infrared spectra and XRD confirms the formation of Hydrotalcite predominantly, however slight changes in
bonding environments of these Hydrotalcite samples are observed. The main bands observed for these
samples are carbonate in calcium carbonate species and Hydrotalcite. Reference spectra of sodium carbonate
and a synthetic Hydrotalcite (Mg
6
Al
2
(OH)
16
(CO
3
).4H
2
O) has been provided in Figure 11 to help with the
interpretation of the Hydrotalcite samples prepared in this investigation. The Hydrotalcite samples prepared in
this investigation are provided in Figure 12.


Figure 11:Infrared spectra of Hydrotalcite and starting materials.



Figure 12:Infrared spectra of Hydrotalcite samples prepared at under different conditions.

The sample Hydrotalcite_6g/L_pH10 initially a sharp band with low intensity is observed at 3694 cm
-1
is
assigned to Mg-OH stretching in magnesium hydroxide (Rives V, 1993; VC, 1974)(confirmed by XRD to be
present in the sample). The broad band observed at 3416 cm
-1
corresponds with OH stretching modes
indicative of hydroxyls in the Hydrotalcite structure and associated water modes. The presence of water in the
structure is confirmed by the appearance of the water-bending mode at around 1600 cm
-1
. The bands observed
at 1449, 1364, 1372 and 863 cm
-1
are indicators of the presence of CO
3
2-
,
(Rives V, 1993; VC, 1974) these
bands are of high intensity and relatively sharp. These carbonate vibration modes are due to carbonate in
Hydrotalcite and calcium carbonate, hence the band at around 1400 cm
-1
shows multiple overlapping bands.
The band at 1365 cm
-1
is commonly observed in Hydrotalcite samples, while the bands at 1449 cm
-1
is typical
of the calcium carbonate precipitates calcite and aragonite(Rives V, 1993). Following this bands with lower
intensity bands are observed at 1093 and 1075 cm
-1
, which is proposed to be Sulphate vibrations indicating the
intercalation of Sulphate in Hydrotalcite. At the end region a group of bands are observed at 743, 687, 533 and
420 cm
-1
with lower intensity and sharpness which are assigned to the multiple metal-oxygen modes in
Hydrotalcite (Mg-O, Mg-O-Al, Mg-O-Mg, Al-O and Al-O-Al).

Presence of Hydrotalcite is confirmed for all samples along with the calcium carbonate species calcite and
aragonite. With respect to magnesium hydroxide a notable trend is followed at band 3694 cm
-1
, which
increased with a decrease in aluminium concentration and increase in pH.























3.

5. ACID STABILITY OF SODALITE AND HYDROTALCITE


5.1.Scale formation:

Scale can be defined as the formation of unwanted deposits inside processing equipment, especially at heat
exchange sites within a plant. In the alumina industry the biggest scaling problem is the formation of sodalite
(aluminosilicate product) during the digestion stage of the Bayer process. The build-up of scales cost the
industry in terms of:
Plant shut-downs
Reduced volume capacity
Reduced heat-transfer efficiency
Lost production
De-scaling operation costs
Health and safety issues surrounding cleaning operations

Sodalite is formed by the reaction of silica minerals in the bauxite ore (generally clay minerals such as kaolin)
and sodium aluminate. Under Bayer conditions (high caustic concentrations and pressures) these silica
minerals dissolve quickly allowing them to react with the sodium alumina (desired product of the digestion
process) as shown in Equation 1:

Equation 1:
6SiO
3
2-
(aq)
+ 6Al(OH)
4
-
(aq)
+ 8Na
+
(aq)
+ X
(aq)
Na
8
(AlSiO
4
).2X.nH
2
O
(s)
,
Where X can be CO
3
2-
, SO
4
2-
, Cl
-
or OH
-
depending on the liquor composition.(J.Addai-
Mensah.M.C.Barnesm R.Jones, 2001)

The rate of aluminosilicate product that forms has been reported to increase exponentially with
temperature(N.K.Kshatriya, 2006), and even though there is generally only about 1% of silica in the digester
the large volumes of ore that are processed only takes a couple of weeks before productivity and efficiency
losses are noticed.

Sodalite scales deposited on metal tubes and pipes throughout the alumina plant can be removed or prevented
by a number of means. Some of these techniques include; magnetic and electric fields, ultrasound, thermal
treatment, mechanical and chemical cleaning. Acid cleaning is a common practice used in industry; however it
has its disadvantages:
Variability of the scale composition on heat exchange surfaces at different temperatures requires
different acid concentrations and reaction times depends on the type of scale that forms:
o Composition
o Thickness
o Texture and structure
o Crystallinity
Corrosion due to residual acid can be mitigated using inhibitors, however this extends the life of the
plant and cannot be fully avoided

This investigation has looked at the formation of sodalite at 130, 140, 150, 160, 170 and 180C to see the
differences in the concentration of acid required for removal. Based on the XRD and IR results in the previous
chapter that sodalite that has been synthesized is predominately a carbonate sodalite structure:
Na
8
(AlSiO
4
).CO
3
.nH
2
O
.
Addai-Mensah et. al.,(J.Addai-Mensah.M.C.Barnesm R.Jones, 2001) reported the
mechanism for scale formation began with the least thermodynamically stable phase to precipitate first
followed by the transformation of the aluminosilicate to more stable products with increased temperatures and
reaction times. The precipitation of aluminosilicate scales in heat exchange sites (greater than 90C) within in
the plant follows the following precipitation and transformation stages:

Aluminosilicate species sodalite aluminosilicate amorphous specie Cancrinite

The acid stability curves for the sodalite samples prepared at 130, 140, 150, 160, 170 and 180C are shown in
Figure 13.The calculations used to convert the volume of acid added to concentration of acid added are
described in Appendix 2.

Figure 13: Hydrochloric acid digestion of sodalite prepared at different temperatures.
The results of the acid digestion tests on the sodalite samples show that the acid stability of
sodalite is to some degree dependent on the temperature that it formed.

If sodalite is written in the following form:
3(Na
2
OAl
2
O
3
2SiO
2
2H
2
O)Na
2
CO
3

the dissolution of sodalite with hydrochloric acid is as follows:
3(Na
2
OAl
2
O
3
2SiO
2
2H
2
O)Na
2
CO
3
+ 26HCl 8NaCl + 6AlCl
3
+ 6Si(OH)
4
+ 7H
2
O + CO
2


Sodalite synthesized at 130C showed the highest resistance to acid digestion, requiring around
115 mmol/L of acid to achieve a pH of 1.5. Increasing the synthesis temperature to 160C showed
a gradual decline in the stability of the resultant sodalite structures, with a reduction of around
25mmol/L of acid being required to achieve the same amount of dissolution. For sodalite prepared
at synthesis temperatures of 170 and 180C, require additional acid indicating that a phase
transformation of sodalite has occurred at these elevated temperatures which improved the
stability of the resultant structure. In order to achieve a pH of 1.5, 98 and 90 mmol/L of acid is
required, respectively. Overall, sodalite prepared at 130C had the greatest stability during the
addition of 0.5M hydrochloric acid, while sodalite prepared at 150 and 160C had the lowest acid
stability. Therefore, in order to minimize acid cleaning costs the temperature of digestion should
be maintained at between 150-160C.
5.2.Land remediation
One of the greatest challenges for the use of bauxite refinery residues is its high alkalinity, and to
mitigate the risk of environmental impacts a number of refineries use seawater to neutralize the
residue. The addition of seawater results in the formation of Hydrotalcite-like structures
(Mg
6
Al
2
(OH)
16
(CO
3
) 4H
2
O), which traps residual caustic in the formation of the Mg, Al hydroxyl
layers:
6MgCl
2(aq)
+ 2NaAl(OH)
4(aq)
+ 8NaOH
(aq)
+ Na
2
CO
3(aq)

Mg
6
Al
2
(OH)
16
(CO
3
2-
)xH
2
O
(s)
+ 12NaCl
(s)
Apart from the precipitation of Hydrotalcite, calcium carbonate (calcite and aragonite), thenardite
(Na
2
SO
4
), halite (NaCl) and a number of minor mixed carbonate species can form during the
seawater neutralization process.

The initial rapid decline in pH after the addition of 4 mmol/L of hydrochloric acid (Figure 14) is
due to the initial stages of CaCO
3
dissolution (Equation 2), which forms calcium chloride and
carbonic acid. Carbonic acid then breaks down to form carbon dioxide and water (Equation 3).
Gas evolution from the surface of the Bayer precipitate was observed during the addition of acid,
which confirms the formation of CO
2
and thus the dissolution of CaCO
3
.

Equation 2: Dissolution of CaCO
3
with hydrochloric acid:
CaCO
3(s)
+ 2HCl
(aq)
CaCl
2(aq)
+ H
2
CO
3(aq)

Equation 3: Dissolution of carbonic acid
H
2
CO
3(aq)
CO
2(g)
+ H
2
O
(l)

During the dissolution of CaCO
3
the Hydrotalcite breaks down into its magnesium and aluminium
hydroxide species (Equation 4). The dissolution of Mg(OH)
2
and Al(OH)
3
is believed to occur
below pH 5.5, whereby magnesium hydroxide reacts to form Mg
2+
ions (Equation 5) while
aluminium hydroxide reacts with acid to form the soluble Al(OH)
4
-
, Al(OH)
2
+
and Al(OH)
2+

species (Equations 6 to 8).

Equation 4: Decomposition of Hydrotalcite with acid(Allada, Navrotsky, Berbeco, & Casey,
2002)
Mg
6
Al
2
(OH)
16
(CO
3
) 4H
2
O
(S)
+ 12H
+
(aq)
6Mg
2+
(aq)
+ 2Al(OH)
3(s)
+ CO
2(g)
+ 15H
2
O
(l)

Equation 5: Dissociation of magnesium hydroxide with acetic acid
Mg(OH)
2(S)
+ 2CH
3
COOH
(aq)
Mg
2+
[(CH
3
COO)
2
]
2-
(aq)
+ 2H
2
O
(l)


Equation 6: Aluminium hydroxide in solution with a pH>8.5

Al(OH)
3(s)
+ OH
-
(aq)
Al(OH)
4
-
(aq)


Equation 7:

Aluminium hydroxide in solution with a pH 4.4-5.4

Al(OH)
3(s)
+ H
+
(aq)
Al(OH)
2
+
(aq)
+ H
2
O
(l)


Equation 8: Aluminium hydroxide in solution with a pH 3.0-4.7
Al(OH)
3(s)
+ 2H
+
(aq)
Al(OH)
2+
(aq)
+ 2H
2
O
(l)
(ANZECC, 2000; Huang WH, 1972)

The amount of acid required to dissolve Hydrotalcite ranges from 90 to 65 mmol/L of 0.5M
hydrochloric acid for the 6 samples synthesized. Precipitates formed using 6g/L of aluminate was
the least stable of the Hydrotalcite investigated.

Overall, Bayer precipitates are likely to be stable over a wide range of pHs suitable for plant
growth, either in bauxite residue tailings dams or applied as part of a land remediation program. If
the pH of the treated soil remained between 7.5 and 5.5, the amount of aluminium released into
the environment would be below toxic levels for vegetation. Sodium is only released in minor
amounts and would not cause sodic effects. In addition, the magnesium, calcium, and potassium
released during Bayer precipitate and calcium carbonate decomposition may act as a slow release
supply of these nutrients, which would support plant growth. Given that rhizosphere
concentrations of organic acids are typically in the range of 0.5-10 mol/L(Dl, 1998) (1000 times
lower than required for the initiation of the decomposition process of Bayer precipitates ), the
dissolution process would be very slow. The use of Bayer precipitate in land remediation could
also assist in neutralizing acidic soils through cation exchange processes involving magnesium
and calcium released.







Figure 14: Hydrochloric acid digestion of Hydrotalcite samples prepared at under different conditions.
6. OPTIMISATION OF ALUMINUM DIGESTER DESI GN

In the Bayer digestion process, there are also two types of digesters used 1) tube digesters and 2)
autoclave digesters. The working of both the digesters is almost similar, which is creating higher
temperature and pressure for digestion of the bauxite slurry. The difference lies in their shape, volume
and optimum conditions used. Generally Autoclave is used in bigger plants because of its volume,
design simplicity, and larger production capacity compared to tube digester.

Figure 15 Tube Digester (google, 2013)


Figure 16 Autoclave digester. (google, 2013)
Table 5 Differences between Tube and Autoclave Digester
Items Tube Digesters
Autoclave in Series
No Agitators With Agitators
Slurry flow types Plug Irregular Back mixing
Average digestion time Shorter Longer Longer
Pump pressure Higher Lower Lower
Digestion time distribution Same, no distribution No regulation
Homogenous, some
distribution
Caustic concentration change Homogenous change Not homogenous
Almost same in every
autoclave
Scale effects on digestion Greater Smaller Smaller
(Don Donaldson, 2013)
Compared to tube digesters, autoclave digesters are generally preferred in the industry because of
increased residence times. The average digestion time, digester volume and extraction efficiency are
much greater in an autoclave digester than the tube digester. Comparisons of the differences between
the two types of digesters are outlined in Table 5. The digestion time in a tube digester is very limited
due to the small volume of tubes, and as a result higher digestion temperatures and pressures are
required to digest the aluminium oxy/hydroxides in the ores. However, raising the temperature is
limited by the design of digester tubes and pumps due to the increased pressure within the digester. In
addition, any small amount of scale formed on the walls of the digester will shorten the digestion time
greatly because of the small volume of tubes. Advantages of an autoclave digester are its increased size,
temperature and pressure tolerance, and the option for it to be designed with or without an agitator.
Digesters with mechanical elements, such as an agitator, generally have problems associated with
scaling. Another major problem of the autoclave digester design, is the fact that large ore particles fall
rapidly to the bottom of the vessel and through the outlet without being fully digested. Therefore, there
are disadvantages to both digester designs with the primary problem being the formation of scale on the
walls or mechanical elements and small residence times that result in the incomplete digestion of the
ore(Don Donaldson, 2013).

The primary problem that affects the lifetime and efficiency of the digester is the precipitation of
sodium aluminosilicate crystals from spent Bayer liquor. Scale can form on the digester walls, heat
exchanger vessels and piping throughout the alumina refinery, with other types of scale forming
downstream from the digester depending of the chemical compositions of the liquor (e.g., calcium
titanate-containing scale and alumina trihydrate scale). The formation of scale leads to a significant
reduction in heat transfer efficiency, resulting in increased energy and caustic soda consumption and
loss of productivity. A traditional digester vessel relies on a rotating agitator to create optimum flow
patterns within the vessel in order to reduce the build up on the vessel walls while establishing
optimum residence time for digestion. The various mechanical elements involved, in particular the
agitator, are exposed to elevated temperatures and high caustic concentrations that favor the formation
of scale. Therefore, they tend to seize before completion of the vessel operating cycle, which is
typically between 6 to 12 months, and require extensive de-scaling and maintenance during shut down.

In order to minimize scaling rates some changes can be made to the design of the digester and include
optimizing the aspect ratio (ratio between height and width), inlet valve size and the implementation of
a steam injection system. The hydrodynamics of the digester is complex with multiphase flow and
liquid-solid reactions. By employing computational fluid dynamics (CFD) system to investigate and
predict the performance of the digester during the initial design, many of these complexities are taken
into account. An in-depth study by (Kumaresan et al., 2009)showed how the CFD system, the residence
time distribution (RTD) and flow patterns could be analyzed by ANSYS CFX11 (computational fluid
dynamics software). A 3D single phase, steady state k turbulence model can then be used to
simulate the flow pattern followed with an RTD study. The flow patterns in a column and tank digester
were compared against different designs; base column, agitated column, modified column, base tank
and baffled tank (Figure 17). In this CFD modeling investigation a lithium ion tracer was used to
validate the model.

Figure 17 A) Base column B) Agitated column C) Baffled column D) Base tank D) Baffled tank. The arrows in the figure show the
direction of slurry.(Kumaresan et al., 2009)
In this investigation, only the digester column is considered because of its higher digestion capacity and
efficiency (based on better aspect ratios). This study showed that factors like strength of trailing
vortices, bulk downward flow pattern, back-mixing by recirculation, and the effect of central core
downward channeling had the greatest impact on the fluid dynamics in the base, agitated and baffled
columns at different speeds. The results showed that an agitated column at maximum speed had the
highest mean residence time with relatively low dispersion; however it had the highest power
consumption due to the agitator and significant interactions with the wall of the digester increasing its
scaling potential. The mean residence time for the base column was higher than the baffled column
design, but the higher bulk downward flow pattern increased the risk of bigger particles of undigested
alumina getting out of the inlet more often. Slurry flow velocities in the various columns are shown in
Figure 18. Therefore, after compromising on various factors a modified column with a combination of
base column and baffled column designs has been adopted. A comparison between the base and
modified column digester showed relatively similar results; since its design is based on a column with
the addition of baffles.

Figure 18 slurry flow velocity vectors in digesters. A) Base column B) Agitated column- 10 rpm C) Agitated column - 52 rpm C)
Agitated column - 80 rpm E) Baffled column(Kumaresan et al., 2009)


It is worth to note that the variation in the slurry inlet makes a tremendous change with the overall
circulation pattern and RTD response curve (figure 19 & 20). The modified column will have a local
recirculation pattern in the vicinity to the slurry pipe and bulk flow tends to become plug flow as the
slurry proceeds towards the outlet. Also, the volume of bulk downward flow in the core region of the
tank is smaller than the base column. A tangentially upward directed flow can be observed around the
bulk downward flow pattern (at 1/2

the distance of digester height) analogous to the flow seen for the
base column (figure 18 A).

Figure 19 RTD curve in digester(Kumaresan et al., 2009)


Figure 20 Expanded view of RTD curve(Kumaresan et al., 2009)
The mean residence time increased by 6.89% for the modified column compared to the original base
column. However, the dispersion level tremendously decreased by 166% due to the substantial zone in
the modified column having a minimum large recirculation flow pattern. The RTD response curve
(figure 19) for the modified column indicates the late appearance of the lithium tracer in the outlet,
which indicates the absence of extended central core downward channeling. The E- curve for this
design has a comparatively shorter tail indicating the outlet flow has negligible short-circuits (figure
20). In summary, the modified column has an increased mean residence time and smaller dispersion
level and is successfully operating in industry with improved extraction efficiencies(Kumaresan et al.,
2009).
Another investigation by (Outotec/Hatch, 2011)involved the replacement of the agitator from the
traditional digester design and introduced the use of multiple steam inlet values. This method
emphasized the importance of inlet size in the digester. This investigation focused on the use of a 1:10
Perspex digester model, with the experimental tests performed using steam jets to replace the
mechanical agitator.

Figure 21 Inlet nozzle and Steam injection nozzle(Outotec/Hatch, 2011)

Assessment of the flow pattern indicated that reducing the size of the slurry inlet nozzle produced a
strong swirl motion with optimal RTD, which aided the suppression of scale formation and formed a
counter-rotating vortex towards the bottom section of the digester, directing material upwards. The
liquid residence time distribution showed little variation in lengthwise (axial) mixing with the change in
inlet nozzle size (Figure 22).

Figure 22 Residence time distribution graph(Outotec/Hatch, 2011)

Direct steam injection (figure 21) was chosen over indirect heat transfer with several design aspects
taken into account. Although this method was preferable, the possibility of chugging and steam
impingement on the digester wall had to be considered.

Figure 23 Flow regions free turbulent jet flow(Outotec/Hatch, 2011)

A digester with a combination of no agitator, optimal inlet nozzles and steam injection system will have
excellent residence time distribution and extraction efficiency. The demerit of chugging and steam
impingement can be alleviated by proper method of thin film coating in the inner wall of digester. This
coating can also act, as a sensor indicating when servicing is required to remove any scale build-up to
maintain efficiency levels. An antiscaling reagent used in the alumina industry is a silane-containing
polymer (Figure 24). In the digester the silane group is hydrolyzed to the siliconate group, which
interferes with the growth of the sodalite crystals on the walls of the digester. The interference of the
silane-containing polymer on the sodalite growth pattern results in the particles that do form not to be
stable, and will cause them to re-dissolve back into solution. It has been proposed that the siliconate
group formed under Bayer conditions binds with the nuclei of sodalite and prevents it from growing
larger than its critical size and thus re-dissolves leaving the siliconate group intact to bind with another
sodalite crystal(H-L Chen, 2007).



Figure 24:Generic structure of the silane-containing polymer, where X represents a various types of
functional groups.

The implementation of these changes to traditional vessels will result in the following benefits:
Prolong the digester life cycle
Increased productivity
Reduced energy costs
Significant reduction in scale removal and safety concerns associated with cleaning operations
Reduction in labour requirements for maintenance
Reduction in replacement of parts due to corrosion
Reduce caustic consumption (used in the formation of sodalite scale)








7.CONCLUSION

Sodalite and Hydrotalcite were successfully synthesized at different conditions and temperatures. The
synthesized samples were analyzed with Infrared microscopy and XRD to understand their
composition. The synthesized samples were then tested for acid digestion stability to understand their
role in the land remediation process. The acid digestion test revealed that, for the residual alkali to
become toxic to the environment the plants should release thousand times more acid than their normal
routine. Only then the caustic toxic waste from aluminum residue will get dissolved and released to the
environment. As a result of acid digestion test we can clearly understand that we need a large amount of
acid for scale digestion and washing in the digester, which is very expensive and time consuming. As a
saying goes prevention is better than cure, it is always good to prevent scaling rather than planning
for its aftermath. In this project we have also proposed an optimized digester design with a combination
of latest advancements in digester design integrated with thin film coating of silane-containing polymer
which reduces scale formation considerably.

REFERENCES

Alcan, Rio tinto.). from http://www.riotintoalcan.com/ENG/ourproducts/360_making_aluminium.asp
Allada, Rama kumar, Navrotsky, Alexandra, Berbeco, Hillary Thompson, & Casey, William H. (2002).
Thermochemistry and aqueous solubilities of hydrotalcite-like solids. Science, 296(Copyright (C)
2012 U.S. National Library of Medicine.), 721-723.
ANZECC. (2000). Australia and Newzealand national water quality management strategy.
Barnes, Mark C., Addai-Mensah, Jonas, & Gerson, Andrea R. (1999a). The kinetics of desilication of
synthetic spent Bayer liquor seeded with cancrinite and cancrinite/sodalite mixed-phase
crystals. J. Cryst. Growth, 200(1/2), 251-264. doi: 10.1016/S0022-0248(98)01294-9
Barnes, Mark C., Addai-Mensah, Jonas, & Gerson, Andrea R. (1999b). The mechanism of the sodalite-to-
cancrinite phase transformation in synthetic spent Bayer liquor. Microporous and Mesoporous
Materials, 31(3), 287-302. doi: http://dx.doi.org/10.1016/S1387-1811(99)00079-7
Bleam, William F. (2012). Soil and Environmental Chemistry. Burlington, MA: Academic Press.
committee, international aluminium institute health.). from http://www.alueurope.eu/wp-
content/uploads/2010/10/IAI-Background-paper.pdf
Dl, Jones. (1998). Orgaic Acids in the rhizosphere - acritical review. Plant and soil, 205(1), 25-44.
Don Donaldson, Benny Raahauge. (2013). Essential readings on light metals Alumina and Bauxite (Vol.
1).
Fortin, Sbastien, & Breault, Raymond. (2004). Bayer process heat exchangers cleaning efficiency:
optimizing the acid dissolution of sodalite scale.
google, Images digester. (2013).
H-L Chen, D. Spitzer, A. Rothenburg, M. Lewellyn, O. Chamberlain, H. Heitner, F. Kula, Q. Dai, C.Franz
(2007). Sodalite scale control in alumina bayer process. Paper presented at the NACE
international.
H.muller, Jamialahamadi and. (1998). determining silica solubilty in bayer process liquor. JOM.
Hanahan, Colleen, McConchie, David, Pohl, John, Creelman, Robert, Clark, Malcolm, & Stocksiek, Curt.
(2004). Chemistry of Seawater Neutralization of Bauxite Refinery Residues (Red Mud). Environ.
Eng. Sci., 21(Copyright (C) 2012 American Chemical Society (ACS). All Rights Reserved.), 125-138.
doi: 10.1089/109287504773087309
Hind, Andrew R., Bhargava, Suresh K., & Grocott, Stephen C. (1999). Bayer process solids: a review.
Colloids Surf., A, 146(1-3), 359-374. doi: 10.1016/S0927-7757(98)00798-5
Hond, RD, Hiralal, Iwan, & Rijkeboer, A. (2007). Alumina Yield in the Bayer Process-Past, Present and
Prospects. Paper presented at the LIGHT METALS-WARRENDALE-PROCEEDINGS-.
Huang WH, Keller WD. (1972). Geochemical mechanics for the dissolution, transport and deposition of
aluminum in the zone of weathering. Clays clay Miner, 69-74.
institute, International aluminium.). from
http://www.d.umn.edu/~pmorton/geol2350/2007/powerpoints/chemistry.html
J.Addai-Mensah.M.C.Barnesm R.Jones, A.R.Gerson. (2001). the mechanism and kinectics of sodium
aluminosilicate scale formation in Bayer plant heat excahngrs. Paper presented at the
International conference on mitigation of heat exchanger fouling and its economic and
environmental implications.
Johnston, M., Clark, M. W., McMahon, P., & Ward, N. (2010). Alkalinity conversion of bauxite refinery
residues by neutralization. J Hazard Mater, 182(13), 710-715. doi:
http://dx.doi.org/10.1016/j.jhazmat.2010.06.091
Jones, B. E. H., & Haynes, R. J. (2011). Bauxite Processing Residue: A Critical Review of Its Formation,
Properties, Storage, and Revegetation. Crit. Rev. Environ. Sci. Technol., 41(Copyright (C) 2012
American Chemical Society (ACS). All Rights Reserved.), 271-315. doi:
10.1080/10643380902800000
K. Zheng, A.R.Gerson, J. Addai-Mensah. (1997). the influence of sodium carbonate on sodium
aluminosilicate crystallization and solubility in sodium aluminate solutions. journal of crystal
growth(171), 197-208.
Kumaresan, T, Thakre, SS, Basu, B, Kaple, K, Gupta, HP, Bandi, A, . . . Sapra, V. (2009). PERFORMANCE
IMPROVEMENT OF ALUMINA DIGESTORS.
limited, Queensland alumina.). from http://www.qal.com.au/Press_Release/red mud fact sheet.pdf
McConchie, D., Clark, M., Hanahan, C., & Fawkes, R. (1999). The use of seawater-neutralized bauxite
refinery residues (red mud) in environmental remediation programs.
McConchie, D., Saenger, P., & Fawkes, R. (1996). An environmental assessment of the use of seawater to
neutralize bauxite refinery wastes.
McConchie, David, Clark, Malcolm William, Davies-McConchie, Fiona Gaye, & Ryffel, Thomas Hans.
(2004). WO2004005202A1.
N.K.Kshatriya, Das gupta, P.K.N.Raghavan. (2006). A study on scale removal chemical in alumina refinery.
Paper presented at the International conference on non-ferrous metals.
Oeberg, N. C. R., & Steinlechner, E. H. (1996). Red mud and sands handling new thoughts on an old
problem. Light Met. (Warrendale, Pa.)(Copyright (C) 2012 American Chemical Society (ACS). All
Rights Reserved.), 67-73.
Outotec/Hatch. (2011). Innovative Digester vessel design. In Outotec/Hatch (Ed.).
Palmer, Sara J., Frost, Ray L., & Nguyen, Tai. (2009). Hydrotalcites and their role in coordination of
anions in Bayer liquors: Anion binding in layered double hydroxides. Coord. Chem. Rev.,
253(Copyright (C) 2013 American Chemical Society (ACS). All Rights Reserved.), 250-267. doi:
10.1016/j.ccr.2008.01.012
Rives V, Labajos FM, Ulibarri MA, Malet P. (1993). A new-hydrotalcite like compund conatining
vanadium ions in the layers. inorganic chemistry.
Smith, Howard D., & Parkinson, Gordon M. (2005). Seawater Neutralisation: Factors affecting adsorption
of
anionic chemical species. Paper presented at the 7th International Alumina Quality Workshop, Perth,
WA.
Smith, Peter. (2009). The processing of high-silica bauxites - Review of existing and potential processes.
Hydrometallurgy, 98(1-2), 162-176. doi: 10.1016/j.hydromet.2009.04.015
Sparks, Donald L. (2003). Environmental soil chemistry (2 ed.). San Diego, CA: Academic Press.
VC, Farmer. (1974). the infrared spectra of minerals. the minerological society monograph.
Xu, Bingan, Smith, Peter, Wingate, Christine, & De, Silva Lynette. (2010). The effect of calcium and
temperature on the transformation of sodalite to cancrinite in Bayer digestion.
Hydrometallurgy, 105(1-2), 75-81. doi: 10.1016/j.hydromet.2010.07.010



APPENDIX 1: EXPERIMENTAL RESULTS

Tables for acid digestion experiments:

Table 6 HT_6g/L 10 pH
Volume of HCL pH Mass
Initial 9.92 0.256
25 8.51
25 7.72
25 6.12
25 5.72
25 5.61
25 5.14
50 5.02
50 4.87
50 4.72
50 4.36
50 4.23
50 4.08
100 3.73
100 3.55
100 3.42
100 3.3
100 3.27
100 3.08

250 2.93
250 2.68
250 2.54
250 2.47
250 2.36
250 2.23
500 2.21
500 2.04
500 1.97
500 1.84
500 1.71
500 1.7
500 1.63
1000 1.59
1000 1.48
1000 1.4
1000 1.33
1000 1.29
1000 1.2
1000 1.16

Table 7 HT_5g/L 10 pH
Volume of HCl pH Mass
Initial 9.91 0.2556
25 8.4

25 7.12
25 6.6
25 6.15
25 6.01
25 5.92
50 5.56
50 5.18
50 5.05
50 4.94
50 4.85
50 4.74
100 4.63
100 4.34
100 4.27
100 4.14
100 4.12
100 3.99
250 3.62
250 3.38
250 3.14
250 3.06
250 2.99
250 2.85
500 2.75
500 2.51

500 2.36
500 2.25
500 2.16
500 2.05
1000 1.97
1000 1.75
1000 1.62
1000 1.51
1000 1.41
1000 1.38
1000 1.28
1000 1.21
1000 1.18

Table 8 HT_4g/L 10 pH
Volume of HCl pH Mass
Initial 9.96 0.2563
25 9.5
25 8.91
25 7.23
25 7
25 6.42
25 6.06
25 5.97
50 5.54
50 5.47
50 5.38
50 5.28
50 5.12
50 4.88
50 4.76
100 4.25
100 4.12

100 4.02
100 3.83
100 3.63
100 3.53
250 3.48
250 3.03
250 2.83
250 2.67
250 2.5
250 2.36
500 2.22
500 2.12
500 2.04
500 1.97
500 1.91
500 1.84
1000 1.8
1000 1.65
1000 1.55
1000 1.46
1000 1.38
1000 1.32
1000 1.26

Table 9 HT_3g/L 12 pH
Volume of HCl pH Mass
Initial 10.82 0.2527
25 10.35
25 9.95
25 9.62
25 9.27
25 9.02
25 8.78
25 8.59
50 8.4
50 6.97
50 6.52
50 5.97
50 5.76
50 5.52
50 5.47
100 5.39
100 5.14

100 4.88
100 4.67
100 4.56
100 4.33
250 4.1
250 4
250 3.93
250 3.69
250 3.35
250 3.32
500 3.2
500 2.72
500 2.49
500 2.34
500 2.23
500 2.14
1000 1.88
1000 1.75
1000 1.64
1000 1.56
1000 1.49
1000 1.42
1000 1.36
1000 1.31

Table 10 HT_3g/l 11 pH
Volume of HCl pH Mass
Initial 10.32 0.2544
25 10.08
25 9.67
25 9.26
25 8.9
25 8.62
25 8.24
25 7.9
50 7
50 6.44
50 6.13
50 5.95
50 5.9
50 5.84
100 5.67
100 5.48

100 5.35
100 5.3
100 5.26
100 5.21
100 5.07
100 5.05
100 5.01
250 4.59
250 4.2
250 3.75
250 3.54
250 3.27
250 2.66
500 2.44
500 2.23
500 2.08
500 1.98
500 1.75
1000 1.62
1000 1.52
1000 1.44
1000 1.38
1000 1.33
1000 1.29

Table 11 HT_3g/l 10 pH
Volume of HCl pH Mass
Initial 9.86 0.2523
100 8.31
100 8.1
50 7.82
25 7.59
25 7.18
25 6.92
25 6.89
25 6.7
25 6.41
25 6.35
25 6.3
50 6
50 5.73
50 5.65
50 5.6

50 5.52
50 5.45
50 5.4
50 5.33
50 5.27
100 5.2
100 5.06
250 4.85
250 4.6
250 4.33
250 4.12
250 3.6
500 3.04
500 2.66
500 2.48
500 2.27
500 2.16
1000 1.89
1000 1.73
1000 1.61
1000 1.52
1000 1.45
1000 1.39
1000 1.34

Table 12 syn_130 kp
Volume of HCl ph Mass
Initial 10.83 0.2516
100 10.42
100 9.81
100 9.31
100 9
100 8.43
100 6.72
100 5.75
100 5.07
100 4.76
100 4.52
100 4.34
100 4.29
100 4.2
100 4.14
100 4.12

100 4.09
100 4.06
100 3.98
100 3.94
100 3.86
100 3.84
100 3.82
100 3.8
100 3.7
250 3.63
250 3.54
250 3.52
500 3
500 2.81
500 2.61
500 2.5
500 2.38
500 2.3
1000 2.12
1000 2.01
1000 1.86
1000 1.75
1000 1.66
1000 1.58

Table 13 Syn_180 kp
Volume of HCl pH Mass
Initial 11.56 0.2527
100 11.19
100 10.81
100 10.48
100 10.13
100 9.81
100 9.48
100 9.03
100 8.12
100 7.52
100 6.87
100 5.99
100 5.32
250 4.59
250 4.24
250 4.12

250 4.07
250 4.04
250 3.98
250 3.87
250 3.77
250 3.69
250 3.42
250 3.39
250 3.33
250 3.07
250 2.94
250 2.81
500 2.43
500 2.26
500 2.11
500 2.01
500 1.92
500 1.84
500 1.77
500 1.71
1000 1.59
1000 1.48
1000 1.38
1000 1.31
1000 1.24
1000 1.18


Table 14 Syn_170 kp
Volume of HCL pH Mass
Initial 11.53 0.253
100 11.3
100 10.99
100 10.72
100 10.55
100 10.42
100 10.29
100 10.18
100 10.08
100 9.98
100 9.87
100 9.74
250 8.74

250 7.4
250 5.38
250 4.58
250 4.49
250 4.34
250 4.25
250 4.19
250 4.17
250 4.11
500 3.99
500 3.86
500 3.78
500 3.57
500 3.33
500 2.78
500 2.66
500 2.47
500 2.36
1000 2.04
1000 1.8
1000 1.63
1000 1.5
1000 1.4
1000 1.31
1000 1.25
1000 1.18
1000 1.13

Table 15 syn_160 kp
Volume of HCL pH Mass
Initial 11.34 0.2514
100 10.85
100 10.46
100 10.08
100 9.76
100 9.49
100 9.26
100 8.76
100 7.67
100 7.1
100 6.42
100 5.65
100 4.86

100 4.51
100 4.3
100 4.27
100 4.15
250 4.1
250 3.9
250 3.81
250 3.35
250 3.12
250 2.97
250 2.9
250 2.72
250 2.6
500 2.32
500 2.14
500 2.02
500 1.94
500 1.87
500 1.83
500 1.77
1000 1.61
1000 1.49
1000 1.4
1000 1.33
1000 1.27
1000 1.21
1000 1.15

Table 16 Syn_150 kp
Volume of HCL pH Mass
Initial 11.28 0.2521
100 11.22
100 10.68
100 10.26
100 9.83
100 9.47
100 8.92
100 7.84
100 6.57
100 5.47
100 4.82
100 4.54
100 4.45

100 4.27
100 4.18
100 3.87
250 3.46
250 3.26
250 3.38
250 2.88
250 2.76
250 2.67
250 2.57
250 2.48
250 2.46
250 2.4
500 2.32
500 2.27
500 2.16
500 2.08
500 2
500 1.94
500 1.73
1000 1.61
1000 1.53
1000 1.46
1000 1.4
1000 1.34
1000 1.3
1000 1.26

Table 17 Syn_140 kp
Volume of HCl pH Mass
Initial 10.85 0.2514
100 10.58
100 10.03
100 9.43
100 8.84
100 7.8
100 6.52
100 5.15
100 4.86
100 4.57
100 4.38
100 4.15
100 4.1

100 4.08
100 4.04
100 4.01
250 4
250 3.75
250 3.71
250 3.66
250 3.61
250 3.4
250 3.37
250 3.21
250 3.1
250 3.01
250 2.98
500 2.64
500 2.5
500 2.34
500 2.29
500 2.21
500 2.17
1000 1.87
1000 1.65
1000 1.54
1000 1.45
1000 1.38
1000 1.32
1000 1.27

APPENDIX 2: CALCULATIONS FOR ACID CONCENTRATIONS


Step 1: Calculate number of moles added
= [volume of acid x concentration of acid] / 1000

Step 2: Calculate number of moles after each acid addition
= [number of moles of previous sample + number of moles added] / [total volume at that addition
point / 1000]

Step 3: Calculate the concentration of acid added
= Number of moles after each addition x 1000
= mmol/L of acid added