ASIA-PACIFIC JOURNAL OF CHEMICAL ENGINEERING Asia-Pac. J. Chem. Eng.

2011; 6: 921932 Published online 22 July 2010 in Wiley Online Library (wileyonlinelibrary.com) DOI:10.1002/apj.487

Research article

Deposition of hydroxyapatite and calcium oxalate dihydrate on a heat exchanger tube

C. P. East,1 W. O. S. Doherty,1 * C. M. Fellows2 and H. Yu3
1 2

Centre for Tropical Crops and Biocommodities, Queensland University of Technology, Brisbane, Queensland 4001, Australia School of Science and Technology, University of New England, Armidale, New South Wales 2351, Australia 3 Chemical Engineering, Patents Examination and Hearings Group, IP Australia, PO Box 200, Woden, Australian Capital Territory 2606, Australia

Received 17 December 2009; Revised 2 June 2010; Accepted 7 June 2010

ABSTRACT: Most studies on the characterisation of deposits on heat exchangers have been based on bulk analysis, neglecting the ne structural features and the compositional proles of layered deposits. Attempts have been made to fully characterise a fouled stainless steel tube obtained from a quintuple Roberts evaporator of a sugar factory using X-ray diffraction and scanning electron microscopy techniques. The deposit contains three layers at the bottom of the tube and two layers on the other sections and is composed of hydroxyapatite, calcium oxalate dihydrate and an amorphous material. The proportions of these phases varied along the tube height. Energy-dispersive spectroscopy and XRD analysis on the surfaces of the outermost and innermost layers showed that hydroxyapatite was the major phase attached to the tube wall, while calcium oxalate dihydrate (with pits and voids) was the major phase on the juice side. Elemental mapping of the cross-sections of the deposit revealed the presence of a mineral, Si-Mg-Al-Fe-O, which is probably a silicate mineral. Reasons for the defects in the oxalate crystal surfaces, the differences in the crystal size distribution from bottom to the top of the tube and the composite fouling process have been postulated. 2010 Curtin University of Technology and John Wiley & Sons, Ltd. KEYWORDS: fouling; heat exchangers; calcium oxalate; silica; hydroxyapatite; elemental mapping

INTRODUCTION
More than 80% of industrial heat exchangers have fouling problems, requiring extra capacity to cover shutdowns and costly cleaning cycles. World-wide costs associated with heat exchanger fouling (present in oil and gas, chemical, petrochemical, mineral processing, power generation, food processing and pulp and paper) have been estimated at over US$26 billion per year for industrialised countries.[1] Recent efforts across the globe have focused on developing strategies to help ameliorate the problem. From an environmental point of view, the Australian sugar industry currently produces 1100 GWh of renewable electricity abating in excess of 1.1 Mt of CO2 equivalent of greenhouse gases annually. As the juice evaporation performance largely determines the energy efciency of a sugar factory, reduced fouling will improve evaporator station efciency and increase the ability of the factory to produce renewable electricity.
*Correspondence to : W. O. S. Doherty, Centre for Tropical Crops and Biocommodities, Queensland University of Technology, Brisbane, Queensland 4001, Australia. E-mail: w.doherty@qut.edu.au
2010 Curtin University of Technology and John Wiley & Sons, Ltd. Curtin University is a trademark of Curtin University of Technology

During sugar manufacture from sugarcane, claried juice containing 1215% sucrose is passed through a number of evaporator units (heat exchangers) where most of the water is removed. Within each unit (i.e. vessel), the juice is boiled in stainless steel tubes (i.e. calandria), which is heated by circulating steam. Usually the juice passes through 5 units after which it contains 65% sucrose and is then passed to the pans for crystallisation. During the concentration process, the tubes become increasingly fouled as a result of the deposition of inorganic and organic compounds, lowering the heat transfer coefcients and consequent reduction in the thermal efciency of the evaporator station. As a result, the sugar factories have to shutdown regularly so that the scale deposits can be removed and operational efciency restored. The cleaning protocol used to remove the deposit is laborious, time-consuming and expensive. To reduce scaling propensity in the sugarcane and allied industries, low-molecular-weight polymers, e.g. poly(acrylic acid), poly(maleic acid), acrylicmaleic copolymers and polyphosphonic acid inhibit or retard the crystallisation of carbonates,[1] sulfates,[2 5] oxalates[6,7] and phosphates,[8] have been used with mixed successes. In the sugarcane industry, these polymers are not very effective.[9] This lack

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of effectiveness is thought to arise in large part due to the composition of the juice, which contains high concentrations of lattice forming ions (e.g. Ca2+ , Mg2+ , SO4 2 , Al3+ , etc.).[10,11] In order to tailor-make scale inhibitors for the sugar industry and develop costeffective cleaning formulations, the rst objective was to fully characterize scale deposits. Doherty et al .[9,12 16] have used X-ray uorescence (XRF), X-ray powder diffraction (XRD), thermogravimetry/differential thermal analysis, highperformance liquid chromatography, atomic absorption spectrophometry and transmission electron microscopy to determine the composition of scales deposited in sugar mill evaporators. The composition of the scales formed in each factory were found to be signicantly different and to depend on whether they originated from early or later stages of the evaporation process. Calcium oxalate, amorphous and crystalline silica, hydroxyapatite and organic matter were found to be present in most of the scales. These studies were based on bulk analysis, neglecting ne structural features and the compositional proles of layered deposits. Shams El Din et al .[17] used visual, wet chemical analysis as well as spectral investigations [including XRD and energy-dispersive X-ray spectroscopy (EDX)] to characterize scales from ash chambers of high-temperature multi-stage ash distillers, with an approach more detailed than that of Doherty et al .,[14] as an attempt was made to characterise the composition of the layers within the scale. The scales were composed of brucite (Mg(OH)2 ), anhydrite (CaSO4 ) and calcite, and the thickness of the scales decreased with decreasing temperature in the distiller. There was also variation in the proportion of these phases with decrease in temperature in the distiller. Cosultchi et al .[18] attempted to characterise the inner and outer layer of a deposit in a petroleum well tube using X-ray photoelectron spectroscopy analysis, XRD and atomic absorption spectroscopy. The inner layer was a 15 m black and hard corrosion product, while the thicker outer layer of 1 cm was made up of hydrocarbons with a small amount of barium sulfate. Unfortunately, Cosultchi et al .[18] were unable to obtain the entire prole composition of the inner layer. The purpose of this study was to obtain additional information on scale composition, than has previously been reported before, using not only XRF, XRD, scanning electron microscopy (SEM) and EDX but also backscattered electron imaging and EDX elemental mapping. The deposit that was characterised was from a tube from a sugar mill evaporator vessel.

of 1.3 mm) was obtained from the no 4 Roberts vessel of a quintuple evaporator station from a sugar factory in North Queensland, Australia. The scale that deposited on the tube accumulated during 1 month of sugar processing. Typically, juice that is feed to the fourth vessel contains 36% sucrose, 700 ppm Ca, 70 ppm P, 250 ppm Mg, 70 ppm Si, 200 ppm S, 1700 ppm K and 5 ppm Fe. Scales formed in the nos 4 and 5 vessels of a quintuple evaporator set are the most difcult to control and remove. In the no 4 vessel, approximately 40% of the tube height is covered with sugar juice during processing. Steam in a multi-effect arrangement is used to heat the vessel with working pressure in the no 4 vessel of 70 kPa absolute. Scale was cleaned from the evaporator surfaces with ethylenediaminetetraacetic acid tetrasodium salt, NaOH solution and sulfamic acid prior to sugar processing. This cleaning protocol may not have removed all the scale. Four 20 mm sections were cut from each end of the tube (starting 140 mm from the top and the bottom), and another four section from the middle of the tube. A vertical cut was made in the wall of the each section so that it could be bent open to allow easy access to the deposit (Fig. 1). Figure 1 shows how scale aked off the tube surface as a result of the section being bent open. The akes have a juice side (the side of the scale that is in contact with the juice) and a tube side (the side that is attached to the tube wall). The tube sections were washed in distilled water for at least 12 h to remove any residual sugar and then dried at 55 C until they were at a constant weight.

Methods
XRD studies on both the juice side and the tube side of the akes obtained from the bottom, middle and top sections of the tube were carried out using a PANalytical radiation with normal XPert MPD, Cu (1.5418 A) conditions. For bulk analysis, these akes were ground into a powder prior to analysis. To a portion of each powder, 10 wt% of corundum was added as an internal standard so that the proportion of the individual phases

MATERIALS AND METHODS

Materials
A fouled stainless steel calandria tube (dimensions: 54 mm outer diameter, 2 m length and a wall thickness
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Figure 1.

A photo of a tube section with scale deposit. This gure is available in colour online at www.apjChemEng.com.
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could be calculated. The X-ray patterns were indexed based on parameters obtained from the International Centre for Diffraction Data (ICDD) powder XRD card index. The data were analysed using HighScore (v2.2, PANalytical, The Netherlands) for quantitative analysis using Rietveld-based technique. The sum of the concentrations of the modelled phases is subtracted from 100 wt% to give a residue component. This residue is comprised of a non-diffracting component and unidentied phases. As a rst approximation, these components have been grouped as the amorphous portion of the scale. The element composition of the bulk samples was analysed using a Brucker-AXS S4 Pioneer X-ray uorescence spectrometer equipped with an AG Rh 22 (Rhodium anode) tube. Scale akes (on both the juice side and the side adhered to the tube surface) were gold coated and SEM images were obtained using a FEI Quanta 200 Environmental SEM at an accelerating voltage of 15 kV. Scale akes were also carbon coated and examined by EDX using a JOEL JXA-840 (20 kV, 1.0 nA, T3) and Analysis Program (v3.30, JOEL) for elemental composition of the surfaces. In another set of experiments, the akes were set in resins, polished and cross-sections were obtained, which were then carbon coated and examined by EDX. The EDX was used for elemental mapping and spot analysis, where typically ve spots were analysed in an area and the average composition of each element calculated. Mapping provides information on elemental associations that may be missed by spot analysis. EDX elemental mapping was conducted on a JOEL JXA840 (20 kV, 3.0 nA, T2) with a 5 s dwell time at each pixel over a 256 192 pixel grid using Analysis Station (v3.30, JOEL). Typically, 30 scans were used to collect data. However, in some samples, a smaller number of scans (25) were necessary in order for more detailed information on the relative concentrations of the elements that were over exposed in the longer scan time to be captured. For each cross-section image, pixel brightness is proportional to electron density. For each elemental map, the pixel brightness is proportional to the concentration of that element. Intensities are not normalised so it is not appropriate to compare pixel brightness between images.

Table 1. Elemental composition (wt%) of deposit by XRFa .

Tube section Bottom Middle

a

Si 1.8 1.2

Al 0.10 0.10

Fe 0.60 0.50

Ca 30.2 25.6

P 11.7 4.7

S 0.10 0.0

LOF 21.8 49.1

1% error.

RESULTS AND DISCUSSION

Bulk analysis
The total amounts of the major mineral constituents for the bulk samples from the bottom and middle sections of the tube are shown in Table 1. There was insufcient sample for bulk analysis of scale from the top section of the tube. Ca and P are the major constituents of
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the scale samples from the bottom and middle sections of the tube. In addition, there are reasonable amounts of Si and Fe. Al and S were also found in minute amounts. The scale from the bottom section of the tube has higher proportions of all the elements identied in Table 1 compared to the scale from the middle section. Also, the proportion of Ca/P is lower in the scale from the bottom (Ca/P = 2.58 bottom, Ca/P = 5.45 middle) of the tube suggesting a greater proportion of calcium phosphate in the bottom section. The loss on fusion (LOF) recorded for these samples are mainly associated with the volatilisation of organic matter, adsorbed H2 O and water of crystallisation and decarboxylation of the inorganic compounds. The XRD diffraction patterns for the samples (including that from the top section) are given in Fig. 2 as well as the ICDD reference patterns for weddellite, hydroxyapatite and corundum. The peaks increase in intensity from the bottom to the top of the tube. This is due to increase in crystallinity of the crystalline phases and/or an increase in their proportions along the height of the tube. The major phases are hydroxyapatite (Ca5 (PO4 )3 OH), weddellite (i.e. CaC2 O4 2H2 O) and an amorphous material. The proportions of these phases as well as the amorphous content are given in Table 2. The presence of CaC2 O4 2H2 O instead of the thermodynamically stable CaC2 O4 H2 O is due to the presence of the ions citrate (including other organic acids), magnesium, phosphate and silica in juice, which are known to inhibit the formation of the latter.[19] The amorphous component is expected to contain inorganic compounds, proteins, polysaccharides, lipids and degraded sugarcane bre.[14] Using the values of Table 2 to calculate the actual Ca and P contents associated with hydroxyapatite and CaC2 O4 2H2 O and comparing this to the XRF results of Table 1 show that the unaccounted P (up to 35% of the XRF value for the middle section) and Ca (up to 13% of the middle section) are probably associated with the amorphous phase. It is also probable that these elements are associated with microcrystalline compounds with concentrations below the detection limits of the XRD. Based on the XRF and XRD results, it is not possible to identify whether the Si is present as amorphous silica or as a silicate. It should be noted in a previous study by Doherty et al .[14] that the Si in the scale sample from
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Relative intensity (arbitrary units)

(c) - Top

(b) - Middle (a) - Bottom Weddellite (01-075-1314) Hydroxyapatite (01-072-1243) Corundum (01-073-1512)
0 10 20 30 40 50 60 70

2-theta

Figure 2. X-ray powder diffraction spectra of bulk samples (including the internal standard, corundum) obtained from (a) bottom (b) middle and (c) top sections of the tube.

Table 2. Scale components (wt%) of bulk samples as determined by XRDa .

Phase Hydroxyapatite Calcium oxalate dihydrate Amorphous

a

Bottom 60.1 14.6 25.4

Middle 16.6 64.2 19.2

Top <2 94.8 3.2

amorphous silica, calcium oxalate, calcium sulfate and aconitate content increase from the rst to the last vessel.

Surface analysis
EDX and XRD analysis were carried on akes on both the juice and tube sides for the bottom, middle and top of the tube to identify the main phases present on the surfaces of the outermost and innermost layers. It was found that hydroxyapatite was the major phase attached to the tube wall, while calcium oxalate dihydrate was the major phase for the surface in contact with the juice at all juice heights. Typical SEM micrographs for the surfaces of the scales are shown in Fig. 4. The micrograph of the scale attached to the bottom of the tube (Fig. 4A) reveals a uniform coating of ne hydroxyapatite particles distributed on the tube wall. However, on the juice side (Fig. 4B), well-formed tetragonal and bipyramidal crystals (with many voids and pits) of calcium oxalate dihydrate with length varying between 10 and 70 m are embedded in a mesh of irregular microcrystalline particles. There is also a brous material in the oxalate matrix. In the middle section of the tube, the micrograph for the surface of the scale attached to the tube (Fig. 4C) reveals an unevenly distributed meshy hydroxyapatite material with shallow holes and voids. The sizes of these voids ranged from 20 to 30 m across. It is speculated that these voids were left behind by the
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1% error.

the no. 4 vessel from the same factory where the fouled tube was obtained was deduced to be amorphous silica by analysing the heated sample by XRD. Of interest in Table 2 is the trend in composition along the height of the tube. The phosphate and amorphous content decreases from the bottom to the top of the tube, while the oxalate content increases along the tube height. A number of factors are expected to inuence the scale composition and the amount of scale formed along the height of the tube. These includes temperature, pH, solubility limits and sucrose concentration.[20] The bottom of the tube is a few degrees ( C) hotter than the top, and the solubility of calcium phosphate is inversely related to temperature, so the proportion of phosphate in the scale should be higher at the bottom than at the top. The reverse is true for calcium oxalate. The trend observed in a single evaporator tube is similar to what prevails in an evaporator station in a sugar factory that processes sugar cane. As shown in Fig. 3, calcium phosphate and hydroxyapatite in scale decrease from the rst to the last evaporator vessel, while the
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50.0 45.0 40.0 35.0 Percent of scale 30.0 25.0 20.0 15.0 10.0 5.0 0.0 #1 16-20 brix

DEPOSITION OF HYDROXYAPATITE AND CALCIUM OXALATE DIHYDRATE

Silica Organic Calcium oxalate Calcium carbonate Calcium sulfate Phosphates Iron Oxide Aconitate

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#2 24-28 brix

#3 32-35 brix

#4 45-52 brix

#5 65-70 brix

Figure 3. Variation of scale components in an quintuple evaporator station,[21] where brix is the dry solid weight per 100 g of sugar juice.

detaching bubbles around the nucleation sites on the tube surface. Under forced convective and nucleate owing boiling heat transfer regime, bubble formation on certain nucleation sites of the heat exchange surface is observed.[22,23] These holes are replicated in the top section (Fig. 4E) where they are larger. On the juice side of the middle section of the tube, agglomerations of well-formed bipyramidal crystals (2580 m) are shown (Fig. 4D), though voids and pits are still present on the crystal surfaces (magnied further in Fig. 5). Calcium oxalate dihydrate was also the predominant phase obtained in the top section of the tube. However, the main differences are in the crystal size and the number of pits and voids. The calcium oxalate crystals formed in the top section of the tube are bigger than those formed in the middle section, up to 165 m in length but retain the same morphology. The number of pits and voids are smallest at the top of the tube. There is evidence of intergrowth between the crystals in both the middle and top sections of the tube (Fig. 4D and F). A closer look at the voids and pits on the surfaces of the calcium oxalate crystals actually show patterns of pit edges in a scaffolding arrangement (Fig. 5). The sharpness of the pit edges suggests a thermodynamic process rather than a kinetic one. Putnis et al .[24] have shown that a surface topography of etched pits in barium sulfate crystals was due to the dissolution process. It is therefore possible in this instance that the voids and pits result from a dissolution process occurring after the growth process during the crystallisation of calcium oxalate in a sugar mill evaporator tube. This
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may arise as a result of changes in temperature and/or sucrose concentration, which lowers the supersaturation of calcium oxalate,[20] as well as changes in the concentration of the incoming juice. Other factors such as the juice volumetric ow may also impact on the propensity of the defects and probably accounts why the pits and voids are more prominent in the crystals located in the bottom section of the tube than at the top. It may also be stated that the microstructure shown in Fig. 5 could be a result of inhibition on the surface of growing and aggregating crystallites by natural inhibitors in the juice.[25] The calcium oxalate crystals grew in size from the bottom to the top of the tube. The factors mentioned for dissolution process may also be applicable here. The temperature of the juice at the bottom of the tube is hotter than at the top, so rapid crystal growth with the formation of smaller crystals will occur at the bottom section of the tube due to reduced calcium oxalate solubility in line with Doherty and Wrights model.[20] Previous studies have shown that an increase in the wettability of a uid could affect the heat transfer coefcient during nucleate boiling through its effect on nucleation site density on the surface.[26,27] Butterworth and Shock[26] observed that more wettable uids, which have smaller contact angles, as has been observed by Yu[23] with increasing sucrose concentration, are more likely to eliminate cavities on heating surfaces, thereby reducing the number of active nucleation sites available. Broadfoot and Tan[28] found that the sugar concentration increases from the bottom to the top of the tube by up to 9 units. These observations help explain the
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Figure 4. Scanning electron micrographs of scale on (A) bottom tube side, (B) bottom juice side, (C) middle tube side, (D) middle juice side, (E) top tube side and (F) top juice side.

larger crystals of calcium oxalate formed on the top of tube.

Analysis of the cross-section

Surface and bulk analysis does not provide sufcient information on the structure of multi-layer deposits. In
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order to determine whether the scale contains layers and the composition of those layers, SEM backscattering images and EDX analysis of the cross-sections were carried out. Cross-sections were only made for the scales located in the bottom and middle sections of the tube. The scale in the top section, approximately 40 m thick (two layers), was too brittle for a crosssection to be made, consistent with its high crystallinity.
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Figure 5. Scanning electron micrographs of a calcium oxalate dihydrate crystal (left) and inset of the voids and pit edges on the crystal surface (right).

Figure 6. Backscatter micrograph of the cross-section of the scale from the bottom section of the tube and a schematic representation. The large crack in the rst layer is an artefact of sample preparation.

As reported in the previous section, hydroxyapatite was the major phase attached to the tube side, while calcium oxalate dihydrate was the major phase on the juice side. The cross-section of the bottom section shows three layers (Fig. 6). The rst layer (250 m) close to the tube side has a large number of pits/holes. The second layer of 100 m contains porous material, while the third layer of 40 m thick contains crystal aggregates. The EDX data for each of these layers are shown in Table 3. For the rst and second layers, Ca, C, P and O are the main elements implying that hydroxyapatite and organic matter are the major phases. Thus, the porous material is associated with organic matter and calcium phosphates. For the third layer, Ca is mainly bound to O suggesting that calcium oxalate dihydrate is a major phase. Organic matter is also present in reasonable amounts. The higher intensity (i.e. brightness) of the rst layer relative to the other layers means a higher density and/or higher average atomic number of the particles in this layer relative to the others.
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Table 3. EDX average values (wt%) for the elements in the layersb .

Tube bottom Element C O Mg Si P S Ca Fe

a

Tube middle Layer 3 29.3 46.2 0.1 0.1 0.2 0.1 23.4 0.3 Layer 1 35.3 31.6 1.2 2.3 9.1 0.1 19.4 0.4 Layer 2 17.4 51.3 0.0 0.1 0.1 0.0 30.9 0.0

Layer 1 25.6 31.9 0.8 1.4 12.5 0.1 26.2 0.5

Layer 2 45.7 26.6 0.4 0.7 8.5 0.1 17.1 0.3

a An overestimation of 2% for the carbon content since material was carbon coated. b An overall error of 4% for each value.

The cross-section of the scale in the middle section of the tube shows two distinct layers (Fig. 7). The rst layer nearest to the tube side is 2555 m
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Figure 7. Backscatter micrograph of the cross-section of the scale from the middle section of the tube and a schematic representation.

in thickness. The EDX of Table 3 shows that it is predominantly hydroxyapatite. The second layer on the juice side has a thickness of 2550 m and it is predominantly calcium oxalate dihydrate. The calcium oxalate dihydrate crystals forms a cemented mass, unlike the agglomerated crystals in the third layer of the scale in the bottom section of the tube.

Elemental mapping of the cross-section of the scale from the middle of the tube conrmed the EDX data (Fig. 9). It also established a strong association between Si, Mg, Al, Fe and O, suggesting the presence of a silicate compound of similar composition as the one identied in the bottom layer. The proportion of this mineral is higher in the middle of the tube than at the bottom.

Elemental mapping Composite fouling

Elemental maps of the cross-sections of the scales from both the bottom and middle of the tube have been carried out to show the spatial distribution of the elements within the layers in order to conrm the EDX results and establish the association between the elements. Figure 8 shows the maps of the main elements of the scale located at the bottom of the tube. A bright area of the map indicates a high concentration of the element, while a dark area of the map indicates a low concentration of the element. An overview of individual maps conrms the EDX microanalysis results. Calcium (see the brightness) is dominant in all layers. Phosphorus is reasonably dominant in the rst two layers from the tube side leaving little doubt that calcium phosphate is present in these layers. Oxygen is most concentrated in the last layer, which is associated with calcium oxalate dihydrate. Figure 8 also highlights an interface layer between the rst and second layers that was missed by the EDX analysis. This interface does not contain Ca and/or P but is composed of Si and Mg with small amounts of Al, Fe and O. The association of these elements may suggest a Si-Mg-Al-Fe-O silicate compound. This interface layer is also repeated between the second and third layers. A closer look at the rst layer closer to the tube side also shows traces of this compound. It could therefore be that, for this scale Si is present as a silicate rather than as amorphous silica. Further analysis is required to establish the form of Si.
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The diffraction data shows that hydroxyapatite is the major phase at the bottom of the tube, while calcium oxalate dihydrate is the major phase at the top of the tube (Table 2). This is consistent with the trend observed in an evaporator station of a sugar factory, where temperature and sucrose concentration strongly inuence the type of material that is deposited. The lack of silica and the higher proportion of hydroxyapatite in this scale, compared to what is generally obtained in the no 4 vessel (Fig. 2), is probably related to differences in the composition of the juice process stream rather than operating conditions. Doherty et al .[29] have found that the clarication technique used by the sugar factory where the tube was obtained, which is different from the technique used by most Australian sugar mills, results in a higher proportion of P and a lower proportion of Si in the processing juice prior to evaporation. The scale formed at the bottom of the tube is thicker than that formed at the top. It is known that turbulent conditions can enhance scale detachment[30] and the top of the tube is expected to be most turbulent tube section.[28] Also, 40% of the tube height is immersed in juice giving the bottom more contact with the juice than the top. Adding to these two factors the gravimetric effect on particles in solution, the bottom of the tube will be more prone to particulate fouling than the top.
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Figure 8. Elemental maps of the cross-section of scale from the bottom of the tube. Insets show areas of association of Si-Mg-Al-Fe-O.

In addition to the factors previously mentioned (i.e. solubility, wettability of uids and sugar concentration), slower crystal growth is expected at the top of the tube due to the reduced availability of the sugar juice and particulate fouling. Thus, there will be less available
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active sites for secondary nucleation enabling crystals to grow to a larger size. Although the scale that deposited in the tube was obtained after 1 month of processing, the sugar factory conducted one cleaning exercise during this period.
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Figure 9. Elemental maps of the cross-section of scale from the middle of the tube.

The exact date this was performed is not known but occurred 2 weeks after the commencement of the processing cycle. The cleaning formulation used by the sugar factory to remove scale from nos 4 and 5 evaporators is ethylenediaminetetraacetic acid
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tetrasodium salt (Na4 EDTA). Na4 EDTA is ineffective in solubilising hydroxyapatite and silica components of scale but is effective on calcium oxalate dihydrate.[31] This being the case, residual scale rich in hydroxyapatite would remain behind before the start of the 1-month
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processing cycle and is most likely the rst layer identied in the bottom scale sample. This layer then serves as a template for growth to commence during subsequent juice processing. If it is assumed that after 2 weeks of operation, the surface of the scale on the juice side is predominantly calcium oxalate dihydrate, then this component would be removed during the cleaning process with Na4 EDTA, leaving behind the second hydroxyapatite layer for the bottom section and the rst hydroxyapatite layer of the middle and top sections of the tube. It is therefore hypothesised that on a clean tube during a processing circle, a hydroxyapatite-rich layer will be deposited rst prior to the deposition of the calcium oxalate dihydrate-enriched layer. Based on these observations, it is probable that mixed fouling is occurring in the tube with several fouling mechanisms occurring at the same time. Scale can be formed by direct growth both on the surface and in the bulk followed by cementation of the particles onto the surface. Hydroxyapatite and calcium oxalate dihydrate are almost certainly deposited by crystallisation fouling, while silica-rich material and organic matter are deposited by particulate fouling. The SEM micrographs of COD (Fig. 4) show that COD crystals increase in size from the bottom to the top of the tube meaning that particle growth is the dominant mechanism for this compound. The uniform coating of hydroxyapatite along the height of the tube suggests a cementation mechanism. The preferential precipitation of a higher proportion of hydroxyapatite on the tube side is due to inverse solubility effect hydroxyapatite forming preferentially on the hotter tube side. Shams El Din et al .[10] explained the differences in the proportions of the phases in multistage ash desalination distillers similarly, as an effect of temperature on the solubility of the individual phases. The reason for the existence of the interface layer containing high concentrations of Si-Mg-Al-Fe-O is not known. However, it is possible that it was left behind during the cleaning exercise after Na4 EDTA removed the calcium oxalate dihydrate-enriched layer. As this mineral remained intact even after Na4 EDTA treatment, it is more than likely that the elements are covalently bonded, suggesting at least the presence of a silicate compound. However, if the Fe is present as the oxide, the high working pH means that Na4 EDTA would be unable to dissolve it.

the juice. The composition of the scale was found to be different along the height of tube with the proportion of hydroxyapatite decreasing from bottom to the top of the tube, while the reverse was true for calcium oxalate dihydrate. Three layers were identied for the bottom section of the tube, while two layers were found in the middle and top sections of the tube. An interface layer composed of Si-Mg-Al-Fe-O mineral (possibly a silicate) was identied between the rst and second layers of the bottom section of the tube and also between the second and third layers. The interface was also present in the rst and second layers of the middle section of the tube. This is the rst time that a compound made up of Si-Mg-Al-Fe-O has been reported in a sugar mill evaporator scale. It is expected that this rigorous approach used in the characterization of the scale sample will provide additional information necessary for the design of chemical cleaning formulations and scale inhibitors.

Acknowledgements
This work was supported by the Australian Research Council Linkage Research Grant, the Sugar Research Limited, Australia and Mulgrave Central Mill, Australia.

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CONCLUSION
The composition of scale formed in a Roberts evaporator tube from a sugar factory has been determined. Hydroxyapatite was the major phase that adhered on the stainless steel tube wall, while calcium oxalate dihydrate was attached on the outer surface that contacted
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Asia-Pac. J. Chem. Eng. 2011; 6: 921932 DOI: 10.1002/apj