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Recovery Phosphate

This document summarizes a study on recovering phosphate and ammonium from fertilizer wastewater through struvite crystallization in a fluidized bed reactor. The study tested different upflow velocities and found that the lowest velocity of 0.014 m/s removed 98% of phosphate and 77% of ammonium, more than the higher velocities. Scanning electron microscopy and X-ray diffraction analysis confirmed the formation of struvite crystals with a cube shape and purity of 70%. The fluidized bed reactor was effective for nutrient recovery from fertilizer wastewater through struvite crystallization.

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0% found this document useful (0 votes)
78 views4 pages

Recovery Phosphate

This document summarizes a study on recovering phosphate and ammonium from fertilizer wastewater through struvite crystallization in a fluidized bed reactor. The study tested different upflow velocities and found that the lowest velocity of 0.014 m/s removed 98% of phosphate and 77% of ammonium, more than the higher velocities. Scanning electron microscopy and X-ray diffraction analysis confirmed the formation of struvite crystals with a cube shape and purity of 70%. The fluidized bed reactor was effective for nutrient recovery from fertilizer wastewater through struvite crystallization.

Uploaded by

Yuni Hapsari
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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IAETSD JOURNAL FOR ADVANCED RESEARCH IN APPLIED SCIENCES ISSN NO: 2394-8442

Recovery of Phosphate and Ammonium from Fertilizer Wastewater


by Struvite Crystallization in a Fluidized Bed Reactor

Yessie Ardina Kusuma #1, Warmadewanthi *2


#*
Department of Environmental Engineering, Faculty of Civil, Environmental, Geo Engineering, Institute Technology
Sepuluh Nopember (ITS), Sukolilo, 60111 Surabaya, Indonesia
[email protected]
[email protected]

Abstract— The fertilizer industry is one of the industries which produce wastewater containing high concentrate of phosphate and
ammonium. Technology for wastewater management is needed to prevent eutrophication as well as conserve the availability of
phosphate in nature. Crystallization process using fluidized bed reactor is so effective in removing and recovering phosphate and
ammonium into the advantageous struvite crystal which contains slow release nutrient. One of the factors that affect the struvite
crystallization process is the upflow velocity. In this research, the lowest upflow velocity of 0.014 m/s was able to remove the phosphate
and ammonium as many as 98% and 77% as well as produce more struvite crystal. The lower the upflow velocity, the more it could
increase the efficiency of phosphate and ammonium removal. Struvite crystals formed based on SEM-EDX had a cube shape with a flat
surface. The main constituent elements of struvite are N, P, O, and Mg. The purity of struvite crystals based on the results of XRD
analysis was as high as 70%. The results of this study showed that the process of struvite crystallization in the fertilizer wastewater
using a fluidized bed reactor was very effective to be implemented.

Keywords— Phosphate, Ammonium, Recovery, Struvite, Fluidized bed crystallizer

I. INTRODUCTION
Phosphate rock is the main ingredient in the chemical industry, where 79% phosphate was used as fertilizer material, around
11% as some feed additive and 7% as detergent ingredients [1]. Despite the advantages of phosphor and nitrogen, both are also the
main causes of eutrophication which could lead to biodiversity loss and water quality problems [2]. Excessive nutrition in lake and
pond causes turbidity and odor in water, increases phytoplankton growth, decreases DO (Dissolved Oxygen) which causes anoxic
conditions and the occurrence of deoxygenation of aquatic plants that causes the fish death [2], [3]. The function of phosphate
recovery technology was to not only prevent the eutrophication but also provide limited natural resources [4], [5]. Crystallization
process technology using magnesium in the fluidized bed reactor was chosen because of the small land use, did not produce
sludge in the processing effluent, was able to remove PO43- and NH4+ in wastewater and produce struvite as the preferred fertilizer
[4], [6].

Struvite or Magnesium Ammonium Phosphate Hexahydrate (MgNH4PO4.6H2O) was a white crystalline substance consisting of
the same molar concentration of magnesium, ammonium, and phosphate [7]. The formula (Eq1) is the reaction between Mg, PO4,
and NH4 in forming struvite:

Mg2++NH4++PO43-+6H2O MgNH4PO4.6H2O (1)

Several factors that affected the crystallization process in the fluidized bed reactor were the saturated solution degree, upflow
velocity, stirring, molar ratio, pH, seed material and reactor shape configuration [6], [9]. The presence of ionic impurities can also
interfere with the formation of struvite crystals, for example, fluoride and calsium [4], [10]. Wastewater containing 600-1500
mg/L fluoride concentrations could interfere with the struvite crystal morphology that eventually created amorphous and irregular
crystal form and had low struvite purity rate [10], [11]. The presence of calcium could cause struvite crystal structural changes and
the morphology to be irregular. Calcium could interfere with struvite crystallization by reducing the size and inhibiting the crystal
growth [12].

The ratio of the molar ratio between [Mg2+:NH4+:PO43-] in struvite formation is 1:1:1. The molar Mg2+ ratio must be higher than
PO43-, because it can increase phosphate removal [13], [14]. Addition of magnesium with Mg/P ratio of 1.5 not only could
increase phosphate removal efficiency by 28% but also increase the cost of purchasing reagents [13], [15]. The upflow velocity of
wastewater in the fluidized bed reactor also had an impact in phosphate and ammonium removal as well as the struvite formation.
The higher the upflow velocity, the more increase of phosphate removal, where the upflow velocity of 400-410 cm/min could
remove the phosphate by 75-85% [8]. The purpose of this study was to determine the removal and recovery of phosphate and
ammonium from fertilizer wastewater by struvite crystallization using a fluidized bed reactor. The investigation will focus on the
effect of upflow velocity

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II. MATERIAL AND METODHS


In this research, the researcher used the wastewater from the fertilizer industry with the following characteristics: 5954.84 mg/L
phosphate, 663.67 mg/L ammonium, 211.3 mg/L fluoride and pH 8. Magnesium as a precipitating agent implemented in this
research was MgCl2.6H2O with a [Mg2+]:[PO43] ratio of 1.5:1. The molar ratio of [Mg2+:NH4+: PO43] in the fertilizer wastewater
was 1.5:1:1.7. The addition of NH4OH on the wastewater was needed so that it reached the molar ratio of [Mg2+:NH4+:PO43] as
much as 1.5:15:1. The seed materials in this study were silica sand and the size was 30-60 mesh. It was chosen to be implemented
in this study because of its inert and resistant properties in wastewater with acidic conditions [2], [13]. The pH adjustment was
done so that the pH during the fluidization process takes place in the range of 8-9. PH adjustment was done by adding NaOH and
H2SO4.

NH4+, PO43- and fluoride concentration were measured using spectroquant Nova 60A. The precipitates produced from the
crystallization process will be separated from the solution and dried at room temperature for 48 hours. Dry precipitates then
analysed by using Scanning electron microscope (SEM) and Energy Dispersive X-ray spectroscopy (EDX) (Hitachi
FlexSem1000). The purpose of using SEM-EDX was to determine the chemical composition, surface characteristics as well as
precipitate morphology and structure. X-Ray Diffraction analysis (XRD) (Phillips Xpert Pro) was done by using Highscore Plus
Analysis software. XRD was used to determine the intensity of the crystal peak formed.

The reactor designs are shown in Figure 1. The reactor used in this research was fluidized bed reactor with 3 vertical
compartments. The dimensions of the three compartments of fluidized bed reactor were lower compartment (volume 1470 mL,
diameter 50 mm) middle compartment (volume 5030 mL, diameter 80 mm), and upper compartment (volume 1900 mL, diameter
100 mm). The lower and middle compartment was where the fluidization between wastewater and sand silica seed materials take
place. The upper compartment was used as a space to prevent the seed materials from being thrown out into the effluent storage.
The reactor was made of acrylic material, equipped with a peristaltic pump to drain wastewater and precipitate MgCl2 into the
reactor. Magnesium was added to the wastewater with a water discharge of 1.6 L/min, 2.4 L/min and 3.2 L/min. Fluidisation
reaction inside the fluidized bed reactor lasted for 70 minutes with a upflow velocity variant of 0.014 m/s, 0.02 m/s and 0.027 m/s.

Fig. 1 Fluidized bed reactor with 3 vertical compartment


III. RESULTS AND DISCUSSION
One of the factors that affect struvite crystallization process using fluidized bed reactor was upflow velocity. The result can be
observed in Figure 2, which explain that phosphate and ammonium removal affected the upflow velocity. The highest phosphate
and ammonium removal rate was 0.014 m/s. it showed that the lower the upflow velocity, the more increase the phosphate and
ammonium efficiency rate. Phosphate removal efficiency on Figure 2 from the upflow velocity of 0.014 m/s to 0.02 m/s and 0.027
m/s, which were 98%, 95%, and 91%, while the ammonium removal was 77%, 75% and 73%.

On the previous study, it was known that the higher the upflow velocity, the more increase of phosphate removal, where the
upflow velocity of 400-410 cm/min can remove the phosphate by 75-85% [8]. On the other research, it was found that the greater
the mechanical stirring energy with a speed gradient of 33 S-1 and 76 S-1 can increase the efficiency of phosphate removal by 80.2
and 91.9% [13]. The result of this study was different from both studies, it was because fluidization process on the top velocity of
0.027 m/s occurred faster than other two velocities (0,014 m/s and 0.02 m/s) so that it affected the reduction of phosphate and
ammonium removal. The velocity could give adequate energy for struvite crystal growth but could also give negative effect when
the velocity was too high. The possible negative effect was that the already formed nucleus can be split into smaller struvite
crystal that decreased the phosphate removal efficiency [13].

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Nucleation was formed based on the initial stirring, while the crystal growth was based on the stirring energy [16]. In this
research, the higher the upflow velocity, the more its ability to increase the stirring energy in the reactor so that the time induction
can be decreased and eventually nucleus crystal formation can occur faster. But, since the Hydraulic Retention Time was shorter,
the already formed nucleus crystal could not grow optimally because the velocity energy was too high. This was in line with the
previous study explaining that phosphate removal efficiency could be increased if the velocity and stirring time was increased as
well [17]. The induction time was the time needed from the initial reaction until the occurrence of supersaturation, which was
when the pH began to be lower and the crystal started to form [18]. In this research, it was found that phosphate removal
efficiency began to increase at the 5th minute. pH decreasing also occurred simultaneously at that time. The pH decreasing was a
sign that the induction time occurred at the first five minutes since the initial fluidization with 0.014 m/s upflow velocity. The
utilization of silica seed materials was also a factor that can increase the phosphate removal efficiency. It was because seed
material could provide a sufficient surface for nucleus attachment and crystal growth [13], [15].

Fig. 2 Phosphate and ammonium removal as affected by upflow velocity

The precipitate that produced from crystallization process using fluidized bed reactor was as much as 9.33 g/L with the upflow
velocity of 0,014 m/s. The result of Scanning Electron Microscopy (SEM) analysis to understand the surface characteristics or
precipitate crystal shape morphology can be observed in Figure 3. The shape of the struvite crystal shape resembles the shape of a
cube with a flat surface. It looked like cube-like crystal shape on the previous research [19]. The flat surface of struvite crystal
indicates little or no presence of ionic impurities such as F and Ca2+ that can interfere with the struvite crystal formation [4], [10].
This is aligned with the results of Energy Diffraction X-Ray (EDX) analysis, which shows that at the upflow velocity of 0,014
m/s, the impurity rate of calcium and fluoride was only 0.17% and 1.03%. A high presence of calcium and fluoride can change the
crystal structure and morphology into irregular. Besides, calcium could also interfere with struvite crystal formation since it can
react with phosphate [10], [12]. The result of EDX shown that the main constituent element of struvite was N. P, O, and Mg. The
result of X-Ray Diffraction (XRD) analysis revealed that struvite purity at the upflow velocity of 0,014 m/s with molar ratio of
[Mg2+:NH4+:PO43-] 1.5:15:1 reached up to 70%. The presence of high ammonium concentrate in wastewater was so beneficial in
the formation of struvite at the solid phase [4]. In order to recover phosphate and ammonium to produce struvite crystal, an
optimum pH adjustment was required at 8-9 and a high ammonium concentration setting at the molar ratio [Mg2+:NH4+:PO43-] to
obtain satisfactory processing efficiency and excellent level of struvite purity [4]. If there was no calcium in the crystal precipitate,
the result of SEM, XRD, and chemical compositions would indicate that the recovered product contains almost pure struvite [9].
In accordance with the result of this research which stated that the upflow velocity of 0,014 m/s with molar ratio of
[Mg2+:NH4+:PO43] 1.5:15:1 contained less calcium so that it had a high struvite purity in the XRD result.

Fig. 3 The shape of struvite crystal on the upflow velocity 0,014 m/s

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IV. CONCLUSIONS
Upflow velocity factors could affect the efficiency of phosphate and ammonium removal in fertilizer wastewater. Among the
three flow velocity variations used in this research, the best velocities resulted in the highest phosphate and ammonium removal
efficiency and the highest production of struvite with the best struvite purity. At an upflow velocity of 0.014 m/s, it could remove
phosphate and ammonium by 98% and 77%. The lower the upflow velocity, the more efficient the removal of phosphate and
ammonium. At an upflow velocity of 0.014 m/s, it produced a longer hydraulic retention time in the crystallization process so that
it could increase the struvite production and the phosphate and ammonium removal efficiency. The resulting struvite crystal
product reaches 9.33 grams per Litre of wastewater. The shape of the struvite crystal resembles a cube with a flat surface with
70% struvite purity rate. In accordance with the results of this study that at the upflow velocity of 0.014 m/s molar with molar
ratio [Mg2+:NH4+:PO43-] 1.5:15:1 contains less calcium so that it has a high purity of struvite in the XRD results.

ACKNOWLEDGMENT
The authors would like to thank The fertilizer industry of PT Petrokimia Gresik for sampling wastewater. Authors express
gratitude to all lecturer of Department of Environmental Engineering, Faculty of Civil, Environment, and Geo-Engineering,
Institut Teknologi Sepuluh Nopember (ITS) for every suggestion and viewpoint, as well to all of the government agency that gives
permission and allows us to do this research. The authors would like to thank Institut Teknologi Sepuluh Nopember (ITS) through
scheme Hibah Penelitian Dana Lokal ITS 2018 for funding this research.

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