Effects of Organic Additives on Physical And Chemical Characteristics of Basic Aluminum Sulfate

Effects of Organic Additives on Physical And Chemical Characteristics of Basic

Aluminum Sulfate

Cesar A. Contreras, Satoshi Sugita, Esthela Ramos and Leticia Torres

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AZojomo (ISSN 1833-122X) Volume 2 March 2006

DOI: 10.2240/azojomo0183

Topics Covered
Abstract
Keywords
Introduction
Experimental
Results and Discussion
Effects of Organic Additives on Chemical Composition of BAS
Effects of Organic Additives on Crystallinity and Chemical Structure of BAS
Effects of Organic Additives on Agglomeration Grade of BAS
Conclusions
Acknowledgements
References
Contact Details

Abstract

Basic aluminum sulfate can be prepared by homogeneous precipitation starting from

admixtures of ammonium aluminum sulfate and ammonium bisulfite solutions. Powder
agglomeration problems usually arise in wet precipitation processes mainly at high
concentration of precursors. Some organic additives have been used in order to modify the
physical and chemical properties of the final product during precipitation processes. In this
work, the effects of cationic, anionic and neutral organic additives on the physical and chemical
characteristics of basic aluminum sulfate (BAS) obtained by homogeneous precipitation were
investigated. Dodecylethyl-dimethyl-ammonium bromide (DEA) and chitosan were used as
cationic additives, whereas dodecyl lithium sulfate (DLS) was selected as anionic additive.
Furthermore, poly(vinyl alcohol) (PVA) and poly(ethylene glycol) (PEG) were used as neutral
additives. The products were characterized by Fourier transformed infrared spectroscopy
(FTIR), powder x-ray diffractometry (XRD), thermal analysis (TG and DTA) and scanning
electron microscopy (SEM). The chemical composition and crystallinity of the final product
were not modified by the presence of the studied additives in this reaction media. The basic
aluminum sulfates were amorphous, with chemical composition 2Al2O3·SO3·9 H2O. However,
the morphology and agglomeration state of the final product were modified by the nature of
the used additives. Anionic additive, DLS, produced irregular agglomerated particles. On the
other hand, neutral additives, PVA and PEG, provided particles with low agglomeration state.
The highest effect on dispersion was observed when cationic additives were used. Fine well-
dispersed particles of basic aluminum sulfate were obtained by addition of chitosan during the
precipitation process.

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 Cesar A. Contreras Satoshi Sugita Esthela Ramos and Leticia Torres

Keywords

Organic Additives, Agglomeration, Basic Aluminum Sulfate

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 Effects of Organic Additives on Physical And Chemical Characteristics of Basic Aluminum Sulfate

Introduction
Aluminas have been in use for many years as catalyst, adsorbents, desiccants, abrasives,
plastic fillers as well as fire retardants for many chemical process industries. Aluminas for
water adsorption, which are traditionally known as desiccants, were first introduced in 1932
[1]. Since long time ago, synthetic aluminas have been used in the chromatographic
purification of biological compounds. Recently aluminas have found widespread usage in
applications as diverse as municipal wastes treatment as well as in polymer and
pharmaceutical industries [2].
Alumina chemicals have been applied to treat industrial and municipal waters [3]. On the
other hand, aluminum sulfate is useful as a coagulant for removal of various metals, particles
and undesirable organic compounds from industrial waste water. Alumina trihydroxide
(gibbsite) and monohydrate (pseudoboehmites) also have been accepted as flocculants in
drinking-water. Transition forms of aluminas have been used as adsorbents for removal of
undesirable contaminants in both municipal and industrial waters.
As a result of more stringent conservation requirements large alumina adsorption processes
have been developed for water treatment. Successful new environmental applications of
alumina adsorbents include the removal of phosphate, mercaptan, arsenic, fluoride and
colloidal silica compounds in ground and drinking water [4].
The most important source of aluminum hydroxides is the Bauxite refining plant. More than
94% world alumina production is accounted for by the Bayer process for Bauxite refining. The
alumina product from the Bayer process is usually 99.5% pure with soda (Na2O) as the mayor
impurity [5]. Therefore, when a pure alumina product is required, it must be obtained by
another chemical process that uses pure aluminum salts as a raw material.
The interest to find alternative routes for the preparation of ceramic powders that avoid the
inconveniences of the traditional techniques has been growing. For this reason, the
development of new synthetic routes is required that allow to obtain ceramic powders with
specific properties, such as small particle size, spherical in shape, narrow particle size
distribution, absence of agglomerates and high chemical purity.
One of the most interesting recent developments in the preparation of aluminum hydroxide
and alumina has been the introduction of BAS as monosized alumina precursors with uniform
and controllable morphology. Matijevic [6] originally produced particles that contained an
appreciable amount of sulfate but this contaminant could be exchanged for hydroxide species,
in much the same manner as the one described by Gordon et al. [7], converting the BAS to
hydrous aluminum oxide.
Other researchers have also used basic aluminum salts as high purity alumina precursors.
Cornilsen and Reed studied amorphous basic aluminum succinate and BAS as potential
precursors [8]. Whereas Sacks et al. [9] and Blendell et al. [10] used spherical BAS as the
specific starting material for conversion to alumina.
The BAS studied by the above mentioned researchers, were obtained by homogeneous
precipitation of BAS in aqueous medium. In this case, agglomeration problems of the BAS
particles generally arise, especially when the precipitation process is performed at high
concentrations of aluminum salt. Therefore, under this condition it is difficult to obtain
monosized and non-agglomerated particles.
The use of low aluminum concentration solutions in the precipitation process allows the
preparation of non-agglomerated BAS particles. However, at these low alumina concentrations
the amount of product obtained is too low, from a practical point of view.
In one alternative process to prevent agglomeration, organic compounds are added to the
precipitation medium. Generally, the preparation of mono-dispersed alumina hydroxide by sol-
gel process was achieved, using high alumina concentration and hydroxyl-propylcellulose as a
steric agent to prevent agglomeration.
In this work, the effects of cationic, anionic and neutral organic additives on the physical and

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 Cesar A. Contreras Satoshi Sugita Esthela Ramos and Leticia Torres

chemical characteristics of BAS obtained by homogeneous precipitation were investigated.

DEA and chitosan were used as cationic additives, whereas DLS was selected as anionic
additive. Furthermore, PVA and PEG were used as neutral additives. The products were
characterized by XRD, TA (DTA and TG), FTIR and SEM.

Experimental
The organic additives used in this study were reagent-grade products obtained from Sigma-
Aldrich. The BAS was obtained by the following procedure. The aluminum bisulfite solution
was prepared by dissolving previously precipitated basic aluminum sulfate with sulfur dioxide
in aqueous media. The organic polymers described above were added to the aluminum
bisulfite solution. This solution is added drop by drop to previously heated water with vigorous
agitation. After the total quantity of the solution was added, the solution was stirred for 15
minutes in order to complete the precipitation. The obtained BAS precipitates were separated
by filtration, washed with hot water and dried at 75°C for 24 hours. The solids were
characterized by X-ray diffractometry (XRD) (Model D-500, Siemens, Germany) using Ni-
filtered CuKα radiation. Infrared analysis was performed using KBr pellets and the samples
were run on a Fourier transform infrared (FTIR) spectrometer (Model 1600 series FTIR, Perkin
Elmer, Norwalk, Connecticut, USA). Differential thermal analysis (DTA) and thermal
gravimetric analysis (TGA) of the samples were obtained by heating 20 mg of sample up to
1300°C, at a rate of 10°C/min, in air (Model SDT 2960, TA instruments, New Castle,
Delaware). The morphology of the particles was determined by scanning electron microscopy
(SEM) (Model jsm-35C Jeol, Tokyo, Japan).

Results and Discussion

Effects of Organic Additives on Chemical Composition of BAS

Chemical composition of BAS obtained by homogeneous precipitation in presence of organic
additives was determined by thermogravimetric analysis. Typical TG curve of BAS is shown in
Figure 1. Table 1 summarized the results of thermal analysis.
In TG curve of Figure 1, the mass loss occurred below 800°C corresponds to the loss of water.
On the other hand, the loss weight between 800 – 1280°C can be attributed to the sulfur
trioxide. So, considering the weight losses of the samples, the amount of water, sulfate and
aluminum oxide can be calculated. The chemical formula of BAS with different additives can
be estimated by this method and the values varied in the range of (1.9-2.3)Al2O3 SO3 (8.4-
11)H2O. On the other hand, the chemical formula of BAS prepared without organic additives
was 2Al2O3 SO3 9H2O. Thus, we can conclude that the organic polymers used here have not
effect on the chemical composition of the precipitated BAS.

Figure 1. Typical TG and DTA curves for BAS with additive.

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 Effects of Organic Additives on Physical And Chemical Characteristics of Basic Aluminum Sulfate

Effects of Organic Additives on Crystallinity and Chemical Structure of BAS

The XRD spectra of all BAS samples obtained with different additives show only amorphous
phase (data not shown).
The FTIR spectra corresponding to a typical BAS precipitated in presence of additives
correspond to a hydrated basic aluminum sulfate. The FTIR spectrum in Figure 2 indicates that
the compound was a hydrate, because of the strong and broad absorption band in the region
from 3000 to 3700 cm-1 and the absorption band which peaks at 1655 cm-1 [11, 12].
Furthermore, the strong and broad band centered at 1135 cm-1 and the small shoulder at 998
cm-1 could been assigned to sulfate absorptions (ν3) and (ν1) respectively [11-13]. The strong
and broad absorption band centered at 613 cm-1 probably resulted from the combined
absorptions of sulfate (ν4), the Al-O stretching vibrations and the Al-OH wagging vibrational
mode of molecular water [11, 12]. Therefore this compound corresponded to a hydrated basic
aluminum sulfate, very similar to those obtained and studied by Matijevic [14] and Saks [15].

Figure 2. Typical IR spectrum of BAS obtained with additives.

It should be notice that the additives were not detected in any BAS samples by FTIR
spectroscopy. This is probably due to the small amount of additive adsorbed on the BAS
surface. Non-ionic macromolecules such as polyethylene oxide and polyvinyl alcohol are
linear, flexible molecules with no charge, which adsorb non-specifically on the surface of
oxides. Because the interaction with the surface takes place through hydrogen bonds between
polar functional groups of the polymer chain and the hydroxylated and protonated groups on
the surface, the adsorption density decreases with increasing pH, irrespective of the nature of
the oxide. Furthermore, the affinity of the polymer for the surface will be weaker when the
surface sites are more prone to salvation [16]. In this case, low adsorption of non-ionic
polymers on BAS surface is expected owing to the high solvation energy of aluminum ion
(4700 kJmol-1, 25°C) [17].
Table 1: Results of thermal analysis (TG and DTA) of typical BAS with additive.

Temperature Weight Loss Thermal Effects Decomposition

(°C) (%) (°C) Stage
30-400 30.21 Endo (121 °C) - H2O
400-800 4.68 ---- - H2O (de OH)
800-1000 17.59 Endo (956 °C) - SO3
1000-1280 - 0.9 Exo (1259 °C) - SO3
On the other hand, polyelectrolytes and ionic surfactants absorb more strongly than neutral
molecules on charge surfaces, because the adsorption energy contains an electrostatic
contribution from sites of opposite charge on the polymer and on the oxide. The surfactant is

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 Cesar A. Contreras Satoshi Sugita Esthela Ramos and Leticia Torres

attached to the surface of the particle through electrostatic interaction between the polymer
charged head and opposite charged sites on the solid surface. In this case, the adsorption
density depends on the sign and number of surface charges [16]. Because BAS is positively
charged (+9.0 mV, Z-potential) at precipitation pH, it is expected that the negatively charged
additive DLS will adsorb more strongly on the positively charged BAS than the positively
charged additives DEA and chitosan.
Although DLS additive is not detected on the BAS sample by FTIR at used additive
concentration, when the added amount of DLS is higher than 4%, the precipitated BAS
becomes hydrophobic, i.e. the dodecylsulfate negative ion is adsorbed on the surface of BAS.

Effects of Organic Additives on Agglomeration Grade of BAS

The chemical nature of the organic polymers affects the morphology and agglomeration grade
of BAS. As shown in Figure 3, the precipitation of BAS with DLS produces agglomerates
consisting of fine particles (0.2 μm). Furthermore, irregular plate like particles (>1 μm) were
formed.

Figure 3. Scanning electron micrograph of BAS obtained with DLS.

As described above, this anionic polymer strongly interact with the positively charged BAS.
So, the molecules of DLS are attached to the surface of the solid through electrostatic
interaction between the negative head of polymers and charged sites on the solid of BAS. At
the same time, the hydrophobic tales of polymer escape contact with the water molecules by
adsorbing passively at the surface of the solution. This is the reason why plate like particles
were formed in the air-water interface. This type of additive is not adequate to obtain regular
shape particles.
Cationic additives, such as DEA and chitosan, produced the BAS with fine spherical particles (<
0.5 μm) and lower grade of agglomeration as shown Figure 4.

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 Effects of Organic Additives on Physical And Chemical Characteristics of Basic Aluminum Sulfate

(a)

(b)

Figure 4. Scanning electron micrographs of BAS obtained with additives (a) DEA and (b)
chitosan.

For comparison, the scanning micrograph of BAS obtained without additives is shown in the
Figure 5.
Generally, the precipitated BAS particles without additives are large agglomerates (>10 μm).
In the early stage of homogeneous precipitation, small particles of BAS are produced. Such
small particles are attracted between them with strong force, consequently this produces large
agglomerates. The presence of a cationic polymer, especially polyelectrolyte chitosan,
prevents formation of hard agglomerates or aggregates of BAS through electrosteric
mechanism. Owing to the fact that chitosan polymer has positive charge at the precipitation
pH of BAS, it is adequate to produce fine non-agglomerated particles of BAS.

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 Cesar A. Contreras Satoshi Sugita Esthela Ramos and Leticia Torres

Figure 5. Scanning electron micrograph of BAS obtained without additives.

On the other hand, neutral polymers, such as PVA and PEG, affect the agglomeration state of
the BAS in a lower grade than the ionic additives. This can be attributed to the weak
interaction force between the neutral polymers PVA and PEG with the positively charged
surface of BAS. In this case, the interaction of neutral additives with the surface takes place
through hydrogen bonds between the functional groups of the polymer and the hydroxylated
and protonated groups of the BAS surface [16]. According to the chemical compositions of
PVA and PEG, the first additive is expected to interact more strongly with the BAS surface than
the second one. PVA contains hydroxyl group, which can form hydrogen bonds with the
hydroxilated groups of the BAS surface, whereas PEG contains only ether group which is less
polar than hydroxyl. In Figure 6, the scanning electron micrographs of BAS obtained with
neutral additives can be seen. SEM micrograph of BAS obtained with PVA shows that this
additive exhibits higher effect on the agglomeration grade of the BAS particles, owing probably
to a steric effect.

(a)

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 Effects of Organic Additives on Physical And Chemical Characteristics of Basic Aluminum Sulfate

(b)

Figure 6. Scanning electron micrographs of BAS obtained with additives (a) PVA and (b)
PEG.

Conclusions
Chitosan is the best dispersant for BAS obtained by homogeneous precipitation. All additives
used here could modify the agglomeration grade without modifying the composition and
crystalline grade of BAS. The chemical compositions of BAS slightly vary in the range of (1.9-
2.3)Al2O3 SO3 (8.4-11)H2O. The crystalline nature of all BAS was amorphous. The adsorption
of all additives used here on the surface of BAS solid was not observed by IR spectroscopy.

Acknowledgements
The authors wish to express their gratitude to the Japanese government for supporting this
work through the 21st Century Center of Excellency (COE) Program of the Ministry of
Education, Culture, Sports, Science and Technology.
We thank Juan José Guzman A., Director of the Centro de Investigaciones en Química
Inorgánica for his permission to publish the paper. Juan Balderas P. and Diana Mendoza are
acknowledged gratefully for the technical assistance and instrumental data interpretations.

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Ceramic Bulletin, 63 [2] (1984) 301-310.

16. J. P. Jolivet, M. Henry and J. Livage, “Metal Oxide Chemistry and Synthesis, from Solution to Solid State”, John
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Contact Details

Cesar A. Contreras, Satoshi Sugita and Leticia Torres

Esthela Ramos
CIDEMAC, FCQ
CIQI Universidad Autonoma de Nuevo Leon
Universidad de Guanajuato Guerreo y Progreso s/n
Noria Alta s/n Monterrey N.L.
Col. Noria Alta, Guanajuato, Gto. Mexico. C.P. 64570
Mexico. C.P. 36050

E-mail: cesarcon@quijote.ugto.mx

This paper was also published in print form in “Advances in Technology of Materials and Materials Processing”, 8[1]
(2006) 35-40.

March 2006 | Volume 2 Page 10 of 10 DOI: 10.2240/azojomo0183