J O U RN A L OF E N V I RO N ME N TA L S CI EN CE S 7 4 (2 0 1 8 ) 9 5– 1 0 6

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Aluminum formate (AF): Synthesis, characterization and

application in dye wastewater treatment

Moxi Xue, Baoyu Gao⁎, Ruihua Li, Jianzhang Sun

Shandong Key Laboratory of Water Pollution Control and Resource Reuse, School of Environmental Science and Engineering, Shandong University,
No.27 Shanda South Road, Jinan 250100, Shandong, China

AR TIC LE I N FO ABS TR ACT

Article history: Aluminum formate (AF), a degradable and non-corrosive coagulant, was synthesized from
Received 17 August 2017 aluminum hydroxide and formic acid. Polyamidine (PA), as a coagulation aid, was combined
Revised 11 February 2018 with AF for dye wastewater treatment. AF was characterized by XPS, FT-IR, viscosity, zeta
Accepted 22 February 2018 potential, mass spectrum and XRD, and the flocculation properties of the dual-coagulation
Available online 3 March 2018 system were characterized by FT-IR and SEM. The results showed that COOH, Al2O3-Al and
O2-Al bonds were formed in the AF synthesis process, and AF had a higher molecular weight
Keywords: and higher charge neutralization ability than PAC. The hydrolysates of AF were determined
Aluminum formate to contain Al13 Al11 and Al2, and the components of AF were confirmed to comprise a
Polyamidine mixture including aluminum formate (C3H3AlO6) and its hydrate. When the color removal
Dual-coagulation efficiency reached 100% in jar tests, the optimized dosage of AF/PA was 18.91/0.71 mg/L,
Phase analysis while the optimized dosage of PAC/PA was 21.19/0.91 mg/L. According to the variance
Interaction analysis, the interaction between AF/PA and PAC/PA were insignificant in macroscopic
view. FT-IR spectrum indicated AF captured pollutant by means of C_C_O bond, PAC
captured pollutant by δ _CH, \C_C\ and δ _CH. Overall, although the coagulation
mechanism of AF was different from that of PAC, AF/PA showed better coagulation
efficiency than PAC/PA in dye wastewater treatment.
© 2018 The Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences.
Published by Elsevier B.V.

Introduction dyes from wastewater, such as adsorption, photolysis, chemical

precipitation, chemical oxidation and reduction, and electro-
Dye wastewater is a complex, high-yield and heterogeneous chemical precipitation (Albuquerque et al., 2013). However,
pollutant that has enormous environmental consequences, those technologies are usually not effective at color removal, or
for example, increasing the chrominance in drainage, jeopar- lack practical utilization due to high cost; thus, an efficient,
dizing aquatic life and generating health hazards for humans inexpensive and convenient wastewater treatment system is
(Goncaf. Talu, 2004; Malachova et al., 2013; Palacio et al., 2009; needed for remediation of large amounts of dye wastewater
Salima et al., 2013). Reactive blue (K-GL), which belongs to the (Pathak et al., 2015; Seo et al., 2015). Coagulation could remove
category of reactive dyes, is widely utilized in the textile 90% of dye molecules from dye wastewater, and is potentially
industry because of the tight combination between textile cost-effective given the large volume of output containment
fibers and its reactive group (Şahinkaya, 2013). A number of required (Albuquerque et al., 2013; Furlan et al., 2010; Liang
physical, chemical and biological methods are used to remove et al., 2014).
Various common coagulants such as aluminum sulfate,
⁎ Corresponding author. ferric sulfate, and ferric chloride are currently the most suitable
E-mail address: [email protected] (B. Gao). coagulants for this application. However, chloride and sulfate

https://doi.org/10.1016/j.jes.2018.02.013
1001-0742/© 2018 The Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V.
96 J O U RN A L OF E N V I RO N ME N TA L S CIE N CE S 7 4 (2 0 1 8) 9 5– 1 0 6

have been shown to cause corrosion with the participation of

calcium, which might damage water supply equipment (Mikola 1. Experiment
and Tanskanen, 2015). Compared to aluminum chloride and
aluminum sulfate, aluminum formate has a higher coagulation 1.1. Material
effect and it is able to effectively decrease the corrosive
effect compared to the other counter anions (Hellstén et al., 1.1.1. Synthesis of aluminum formate and PAC
2005; Parrino et al., 2014). Furthermore, formate salts can be AF solution was directly obtained from the reaction of aluminum
decomposed under UV irradiation at 253.7 nm, which would hydroxide and formic acid. The synthesis method was a
avoid the accumulation of anions in wastewater treatment modification of that in a patent application by Bårström et al.
(Goncaf. Talu, 2004). The water containing formate can be used (2008), and this method was adopted by Mikola et al. (2013) as
for irrigation without causing land salinization. However, when it well. The HCOOH to Al molar ratio was set to 3.0 during this
is used in treatment of water supply, formate groups would study.
contribute to the dissolved organic carbon content. As a result, in Firstly, Aluminum hydroxide containing 5.1% (W/W) of
combination with UV light and ozone processes, aluminum aluminum (aluminum hydroxide, reagent grade, Sigma Aldrich,
formate (AF) can be compatible with the treatment process CAS: 21645-51-2), was suspended in UP water. Secondly, formic
(Mikola et al., 2013; Väänänen et al., 2012). In practical application, acid ((98% (W/W), Tianjin Damao Chemical Reagents Co.,China)
AF can be used in wastewater treatment as part of a complete was diluted to 80% in water (W/W), and then added to the
process including coagulation, biological treatment and UV suspension to reach a Al-HCOOH molar ratio of 1/3. After steady
disinfection. Väänänen et al. (2012) reported a method for AF stirring for 2 hr at 60°C, the mixture turned into a translucent
synthesis and its application in water treatment. However, solution (Mikola and Tanskanen, 2015). In this study, PAC was
characterization of this process has been lacking, such as synthesized by titrating sodium carbonate into aluminum
determining the changes of chemical species after synthesis. chloride solution, where the molar ratio of [OH−]/[Al3+] was
Thus, in order to understand the chemical reaction mechanism, adjusted to 2.2, the aging temperature was 25°C and the aging
more powerful proof is needed with additional characterization time was 30 days.
methods.
In addition to the corrosion of equipment by low-molecular- 1.1.2. Preparation of polyamidine
weight aluminum salts, excess aluminum poses a serious threat The synthesis of polyamidine followed the method described
to humans and other living organisms as well (Cheng and Chi, by Guo et al. (2017).
2002; Mena et al., 2013; Roque-Ruiz et al., 2016). Therefore,
efficient coagulant aids have been adopted in water treatment 1.1.3. Preparation of simulated dye wastewater
processes in order to increase the coagulation effect. Many The simulated dye wastewater was obtained by dissolving
studies have provided strong evidence for the improvement of Reactive Blue K-GL powder in tap water, and the relevant
coagulation efficiency using coagulation aids (Lee and characteristics are shown in Table 1.
Westerhoff, 2006; Yang et al., 2011; Ying et al., 2011). Polyamidine
(PA), a cationic polymer containing the amidine unit, has a high 1.2. Characterization
absorption bridging capacity for heavy metal ions and has been
applied in treatment of high-concentration industrial wastewater 1.2.1. FT-IR and XPS measurements to characterize the
(Toktonov et al., 2006). However, there are only a few studies on synthesis process
the coagulation performance of systems utilizing PA. Therefore, The AF powder was achieved by vacuum freeze-drying of the
the application of PA in combination with other coagulants is above-described AF product for 24 hr (−60°C). FT-IR and XPS
worthy of study. In this work, in order to understand the effect of experiments were conducted to observe the chemical variations
PA in the coagulation process, the AF/PA and aluminum occurring during the synthesis process. The reaction mecha-
polychloride (PAC)/PA coagulation systems were studied to nism was revealed by disappearance or formation of chemical
investigate the efficiency of dual coagulation using PA and Al species by comparing results for AF and Al(OH)3.
coagulants. Guo et al. (2015) investigated the role of PA in the
coagulation performance and floc properties in combination with 1.2.2. Intrinsic viscosity and zeta potential measurements for AF
aluminum salts for the removal of natural organic matter (NOM). Characterization methods, such as viscosity and zeta potential
However, the increase in floc dimension induced by PA was not measurements, helped elucidate the difference between AF and
the main mechanism of its function as a coagulation aid, PAC in terms of coagulation behavior. Viscosity measurements
according to Guo et al. (2015). Therefore, more microscopic show the relationship between molecular weight and the
characterization and data analyses are necessary to gain a better intrinsic viscosity of the solution. Generally, organic coagulants
understanding. with higher viscosity have larger molecular weight, as well as
In this study, the synthesis of AF was investigated in detail better coagulation ability. This is because coagulants with large
by rigorous characterization, such as X-ray photoelectron molecular weight can aggregate the pollutants and precipitate
spectroscopy (XPS), Fourier Transform Infrared Spectroscopy more easily. The viscosity of samples with different concentra-
(FT-IR), viscosity and zeta potential measurements. Further- tions was measured by a Ubbelohde viscometer, and the
more, the interaction between AF and PA was exhibited by intrinsic viscosity was calculated by extrapolation to character-
scanning electron microscope (SEM) and statistical analysis. ize the molecular weight of different samples.
PAC was adopted as a comparison in this research to evaluate Charge neutralization, an important property for coagu-
the efficiency of AF. lants, is reflected by the zeta potential. To compare the charge
 J O U RN A L OF E N V I RO N ME N TA L S CI EN CE S 7 4 (2 0 1 8 ) 9 5– 1 0 6 97

Table 1 – Relevant parameters of Reactive Blue (K-GL).

Name Concentration Wave length Absorption Molecular structure
(mg/L) (nm)

Reactive Blue 100 608 1.030 ± 0.03

neutralization ability and adaptability of AF and PAC under system, AF was dosed before PA in the rapid mixing segment,
different pH conditions, the pH of coagulant samples was and the interval was 30 sec. For the PAC/PA system, PAC was
adjusted from 1.6–13.4 using NaOH or HCl, and measured by a dosed 30 sec before PA addition as well. To weaken the effect of
Zetasizer Nanoseries instrument (Malvern Co., Ltd., UK). pH change on coagulation behavior, the UV608 and zeta
potential data were measured after adjusting the pH to 8.16 ±
1.2.3. MS detection for AF and XRD substance identification for 0.05 (initial pH of raw water). The interaction between coagu-
AF lants and coagulant aid was studied by variance analysis, and
The mass spectrum (MS), which can detect samples at low the optimal dosages of coagulants and coagulant aid were
concentrations (mg/L), was able to characterize the hydrolyzed ascertained by a 3D surface model.
coagulants in terms of m/z (mass charge ratio) distribution,
quantity of electric charge and aluminum species present (Bi et 1.4. Floc properties
al., 2013; Feng et al., 2011a; Zhang et al., 2017). To detect the
characteristics of hydrolyzed AF using MS measurements, AF was To demonstrate the interaction between the coagulants and
dissolved in RO water to obtain a dilute solution of concentration coagulant aid, FT-IR spectroscopy was used as an effective
10 mg/L. Then, the AF solution was injected into the MS method to observe the changes in chemical species during the
spectrometer (LCQ Fleet™, Thermo Scientific™). In addition, coagulation process, and the results could provide possible
PAC was measured for comparison in MS analysis, and all the combinations to explain how the coagulant aid functioned in
MS spectrum data were set in positive ion mode. The XRD (X-ray the coagulation process. The sedimentary flocs were freeze-
Diffraction) pattern of the freeze-dried AF powder for scattering dried at − 60°C in a vacuum freeze-dryer for 24 hr, and then
angles (2θ) 5°–90° is shown in Fig. 6. The chemical components of the pulverized flocs were subjected to FT-IR and SEM analysis.
AF were detected by an X-ray fluorescence spectrometer.

1.3. Jar tests 2. Result and discussion

Jar tests were carried out using a program-controlled jar tester 2.1. Characterization of aluminum formate
(Zhongrun Water Industry Technology Development Co. Ltd.),
and each jar in the tests had a volume of 1.0 L. The coagulation In this study, FT-IR and XPS were chosen to measure the
process contained three segments: rapid mixing (200 r/m), slow chemical changes occurring during the synthesis process, and
mixing (40 r/m, 15 min) and sedimentation (0 r/m, 30 min). In the Al-HCOOH molar ratio in AF was selected as 1/3. The XPS
these experiments, the dosages of coagulants and the dosages results are shown in Fig. 1. The main element (Al, C and O)
of PA were designed by Design-Experts (Version 8.0.6) according measurement was able to discriminate the difference between
to response surface methodology. The related parameters and AF and Al(OH)3 by the displacement and proportion of the
designed test units are shown in Tables 2 and 3. For the AF/PA peaks. Because Al2O3·3H2O existed in the form of Al(OH)3, Al2O3
was the sole Al species observed in Al(OH)3. Compared with Al
Table 2 – Results of viscosity measurements. (OH)3, AF showed new chemical species such as AlOx-Al, Al2O3-
Al, O2-Al, Al-HOOC, which suggested that AF was synthesized
C (g/L) t (sec) η ηr ηSP lnηr ηSP/c lnηr/c [η]
successfully. In addition, the XPS result proved the hypothesis
PAC that formic acid not only played a role in adjusting acidity, but
10 421.55 1.179 1.182 0.182 0.167 0.018 0.0167 0.009 also participated in the polymerization of aluminum species by
5 378.82 1.060 1.062 0.062 0.060 0.012 0.012 the formation of Al2O3-Al and O2-Al. This conclusion could also
1 360.21 1.008 1.010 0.010 0.009 0.010 0.009
be demonstrated by the corresponding peaks in the FT-IR
AF 3.0 spectra (Fig. 2). When Al2O3-Al and O2-Al bonds appeared,
10 428.72 1.199 1.202 0.202 0.184 0.020 0.018 0.012 another hypothesis was put forth that the speciation of
5 389.32 1.089 1.091 0.091 0.087 0.018 0.017 aluminum might be more complicated than reported in recent
1 360.91 1.010 1.012 0.012 0.011 0.012 0.011 research. According to Väänänen's work (Väänänen et al., 2012),
RO dimeric aluminum is the dominant species of AF at pH 4, and
356.63 0.9982 1 some trimeric species exist as well. However, although Al2O3-Al
and O2-Al were found in AF, the speciation of AF still needed
PAC: aluminum polychlorid; AF 3.0: aluminum formate for the
further characterization to verify the species present. Al2O3-Al
HCOOH/Al molar ratio at 3.0; RO: reverse osmosis.
and AlOx-Al might exist in complex polymeric forms, and
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Table 3 – Comparison between PAC and AF 3.0 in m/z distribution, positive charge and aluminum species from MS spectral
analysis.
Distribution of m/z (%) 80–300 300–500 500–700 700–1000

PAC 8.27803 2.706951 67.63884 21.37617883

AF 3.0 58.835546 4.085802 20.73544 16.34320735
Distribution of positive charge (%) 1–3 3–9 >9 Unidentified substances
PAC 2.4100594 12.0503 10.02445 75.51519385
AF 3.0 19.509704 3.677222 9.499489 67.31358529
Distribution of aluminum species (%) Al1-Al4 Al5-Al12 Al13-Al16 Unidentified substances
PAC 2.8990569 9.308418 0.279427 87.51309815
AF 3.0 10.214505 21.34831 13.89173 54.54545455

the aluminum hydrolyzation at different pH should also be According to recent research (Ko et al., 2017; Stratiev et al.,
considered. Fig. 1d and e illustrate that the \COO\ group was 2016), intrinsic viscosity ([η]) has a strong relationship with
formed in this synthesis process, which verified that the molecular weight, and coagulants with high intrinsic viscosity
\COO\ group was attached to aluminum and combined into usually have high molecular weight. So, the molecular weight of
stable chemical species, not in a volatile acid (Davies et al., AF samples was characterized by intrinsic viscosity measure-
1991). ments in this study, which could be calculated by extrapolation
As shown in Fig. 2, the Fourier Transform Infrared Spectros- of the plotted data (Hobbs, 1980). Based on previous research
copy (FT-IR) proved the hypothesis that the synthesis of AF not provided by Väänänen et al. (2012), the dominant aluminum
only formed \COOH groups bound with aluminum, but also species of AF dimeric aluminum. Therefore, AF should have a
formed polymeric aluminum species. These conclusions also smaller intrinsic viscosity than PAC, which is constituted by
agreed with the results derived by XPS. The wide peak in the Al species containing 13 aluminum atoms. According to the results
(OH)3 spectrum at 3470 cm−1 represented the \OH group in Al shown in Fig. 3 and Table 2 ([η]PAC < [η]AF3.0), so the molecular
(OH)3 before the synthesis of AF. After the synthesis took place, weight of AF 3.0 (the Al-HCOOH molar ratio of AF was 1/3) was
the peak for the \OH group weakened and the characteristic clearly larger than that of PAC.
peaks of carboxyl groups appeared in the AF FT-IR curve at 3490, Charge neutralization is the most dominant mechanism in
2939, 1616 and 1400 cm−1. The strong peaks at 1616 and the coagulation process of aluminum salts. When a coagulant
1400 cm−1 might suggest vibration coupling of the \COO\ has a higher surface charge, the charge neutralization ability
group, due to delocalization of electrons on the two oxygen is better consequently. As a result, zeta potential was adopted
atoms. In addition, the peak which appeared at 1090 cm−1 as an effective and convenient measurement for optimizing
indicated the existence of R\O\R′ groups. Considering the AF samples. Furthermore, zeta potential measurements could
reaction products, it was possible that Al\O\Al was formed in help in studying the aluminum hydrolysis process over a wide
this reaction system. The Al\O\Al bond provided more pH range. Therefore, the zeta potential of AF samples was
evidence for the existence of polymeric aluminum species in measured at pH ranging from 1.6 to 13.4, with PAC also
the reaction products. This conclusion was in accordance with measured for comparison, to better understand the aluminum
the XPS results suggesting that the polymeric aluminum was hydrolysis process.
formed during the synthesis. According to Fig. 4, the trend of AF curve was similar to
In order to characterize the coagulation ability of AF, the that of PAC in the pH range of 1.6–8.0, except for the higher
viscosity and zeta potential of samples were measured. zeta potential at pH 8.0–13.4, showing an obvious difference

Fig. 1 – X-ray photoelectron spectroscopy (XPS) spectra for Al(OH)3 Al (a), O (b); XPS spectra for aluminum formate (AF) Al (c), O
(d), C (e).
 J O U RN A L OF E N V I RO N ME N TA L S CI EN CE S 7 4 (2 0 1 8 ) 9 5– 1 0 6 99

50
100
40 PAC
AF 3.0
80 R-CH
30
Transmittance(%)

Zeta potential (mV)

60
20

40 R-OH
10
R-COOH

20 0
AF
Al(OH)3
R-O-R' R-CH -10
0 R-OH
R-CO-R' R-OH
4000 3000 2000 1000 -20
0 2 4 6 8 10 12 14
-1
Wavenumbers cm pH

Fig. 2 – Comparison of FT-IR spectra for Al(OH)3 and AF. Fig. 4 – Zeta potential results for the pH range of 1.4–13.6.

between the coagulants in terms of surface electric charge. ability in bridge and sweep flocculation than polymeric
The hydrolysis of aluminum salts showed a complex dynamic aluminum. Generally, highly complex polymeric aluminum,
balance as a function of pH: When the pH was less than 4, such as PAC, has better ability to adapt to a wide pH range
the dominant hydrolysate was Al(H2O)3+, which has a weaker than simple aluminum salts. As a result, the proportion of the
Al(H2O)3+ hydrolysate in PAC is less than that in solutions of
monomers (such as AlCl3) and simple polymeric aluminum
(Al2(SO4)3). Therefore, in Fig. 4, AF presented weak acidic
adaptability, which suggested that AF contained polymeric or
monomeric aluminum hydrolysates. In the pH range of 5 to 9,
Al(OH)(H2O)2+ 4+
5 , Al(OH)2(H2O) , and Al(OH)3 began to appear,
and the zeta potential curve reached a peak. In this condition,
the charge neutralization ability reaches its peak, and the
optimized pH condition is always within this pH region (Wang
et al., 2009). In this region, the trends for PAC and AF were
similar, which indicated that the hydrolysates of AF and PAC
were consistent with those of PAC. Furthermore, both AF and
PAC exhibited better coagulation behavior in the pH range 5 to
9 than in strong acidic (pH < 5) and basic (pH > 9) conditions.
However, in the pH range of 9–13.4, AF was different from PAC.
In alkaline conditions, the dominant hydrolysate of PAC was
Al(OH)−4, which contributed a negative charge to the zeta
potential. The higher zeta potential of AF than PAC indicated
the presence of a different hydrolysis mechanism under these
conditions.
On the basis of the results in Fig. 5, the distribution of
molecular weight, positive charge and aluminum species are
shown in Table 3. Because the test concentration used for MS was
10 mg/L, the substances detected should be the hydrolysates of
the aluminum coagulants. According to Table 3, the hydrolysates
of AF were concentrated in the m/z range of 80 to 300 and the
most intense peak was at m/z 213 (100%). In addition, Al13 species
at m/z 213, 337 and 328 were also detected. Therefore, the
dominant species of AF was found to be Al13. In addition, Al11 (m/z
226) and Al2 (m/z 138) were also detected as main products in the
hydrolysis of AF (Feng et al., 2011b). Based on Sarpola's research
(Sarpola et al., 2007), the Al13 core is very stable and requires a
Fig. 3 – Viscosity results of aluminum polychloride (PAC), AF high collision energy (75 eV) to break its structure. However,
3.0 plotted with concentration as the X axis, and ηSP/C, lnηr/C Zhao's research (Zhao et al., 2009) proved that dimers, small
as Y axis; the intercept of the intersection gives the intrinsic polymers and Al13 could transform into each other during the
viscosity, which can be used to represent weight. hydrolysis and polymerization process of aluminum salts. Thus,
100 J O U RN A L OF E N V I RO N ME N TA L S CIE N CE S 7 4 (2 0 1 8) 9 5– 1 0 6

Fig. 5 – Mass spectrum of AF 3.0 (a) and PAC (b) at 10 mg/L.

the aluminum species of AF could be seen as a series of 2.2. Application of AF in coagulation

transitional species between small polymers and Al13. Accord-
ingly, the mechanism of PAC hydrolysates was more ambiguous To ascertain the optimized proportions for PAC/PA or AF/PA, a
than that of AF. Because of the lack of peaks for Al13 species and central composite design (CCD) (designed by Design-Expert
the appearance of a large amount of unidentified species, the software (version 8.0.6)) was adopted for the response surface
hydrolysates of PAC might aggregate into bigger polymeric experiment. The relevant parameters are shown in Table 4.
amorphous hydroxide species (Zhao et al., 2015). The phase The dosage of coagulant and dosage of PA were designed as
compositions of AF and PAC were determined by XRD, and arguments respectively. The dye removal efficiency and zeta
results are exhibited in Fig. 6. Based on Fig. 6, the composition potential were set as dependent variables, and each numeric
of AF was identified as a mixture including aluminum formate factor was varied in 5 levels. According to the design requirement,
(C3H3AlO6), aluminum formate hydrate (C3H3AlO6·3H2O) and 12 jar test groups were needed in this design, and the methods
aluminum hydrogen formate (C3H3AlO6·2H2O2). By comparison, and results of the design are listed in Tables 5 and 6, respectively.
PAC was deemed to be a mixture dominated by aluminum For visualization of the coagulation type differentiation, the
chloride (AlCl3). dosages for both PAC/PA and AF/PA were executed as the design
 J O U RN A L OF E N V I RO N ME N TA L S CI EN CE S 7 4 (2 0 1 8 ) 9 5– 1 0 6 101

Table 5 – Results of jar test of PAC combined with PA.

No. Dosage of Dosage of Removal Zeta potential
PAC (mg/L) PA (mg/L) efficiency (%) (mV)

1 19 1.25 93.123 −20.8

2 19 1.25 94.556 −19.2
3 8 2 17.574 −19.85
4 19 1.25 94.174 −18.3
5 3.443651 1.25 0.621 −19.75
6 19 1.25 95.033 −21.25
7 19 2.31066 91.117 −21.3
8 19 0.18934 93.314 −19.55
9 30 2 97.947 −13.4
10 8 0.5 18.72 −19.5
11 34.55635 1.25 98.567 −10.305
12 30 0.5 98.185 −13.4

the optimized dosage was 21.19/0.91 mg/L, and the dye removal
efficiency reached 99.9%. Compared with the PPA^2 value
(0.2336), the smaller PPAC^2 value (0.0002) suggested that PAC
offered a stronger effect in the coagulation process. Corre-
spondingly, the optimized AF/PA dosage was 18.91/0.71 mg/L,
where the removal efficiency was 99.9%. Due to the lower
p-value of AF (PAF^2 = 0.0049, PPA^2 = 0.6942), the dominant
Fig. 6 – The X-ray diffraction analysis results of PAC and AF factor was AF in the AF/PA system. For the same removal
3.0. efficiency, both the dosage of AF and dosage of PA added were
less than the dosages of PAC/PA. The comparison between the
PAC/PA and AF/PA systems revealed that AF had a better
coagulation effect in reactive dye wastewater treatment, and
specified, using variance analysis to judge the interaction the combination of AF and PA was better than PAC/PA.
between the coagulant and coagulation aid and compare the According to Fig. 8, the 2D removal efficiency graph could
coagulation effects between AF and PAC (Tables 7 and 8). show the effects of the coagulant and coagulation aid
The correlation result of the designed model could be separately. The color removal efficiency on Line A or Line B
represented by the p-value: if the p-value is less than 0.05, it could provide the separate effect of the coagulant aid (PA) or
can be seen that the entire model is significant in accordance coagulant on the coagulation process. For example, the data
with the 5% confidence interval in the analysis of variance. parallel with line A represent the influence of PAC on the
The smaller the p-value, the higher the model significance, coagulation process; the data parallel with line B represent the
which means that the fit of the equation is better. Based on influence of PA on the coagulation process. According to the
the p-values in Tables 7 and 8, the model was in accordance 2D graph, we found that the effect of the coagulation aid was
with the significance testing. Therefore, the design was insignificant in the PAC/PA and AF/PA systems, and that the
reliable. Apart from judging the reliability of the model, coagulant aid in the PAC/PA system shows better coagulation
variance analysis could be used to analyze the interaction ability than PA in the AF/PA system. However, the better
between the coagulant and coagulant aid. If the p-value of A*B separate effect of PA in the PAC/PA system might not reflect
is less than 0.05, it can be seen that the coagulant and better color removal efficiency for the PAC/PA system. AF/PA
coagulant aid (factor A and factor B) have coefficient interac-
tion. However, both PAC/PA and AF/PA revealed no coefficient
interaction (PPAC⁎PA = 0.9567, PAF⁎PA = 0.8039). Although the
Table 6 – Results of jar test of AF combined with PA.
interaction was insignificant, PA still showed a positive effect
in the coagulation process, which will be discussed further on NO. Dosage of Dosage of Removal Zeta potential
AF (mg/L) PA (mg/L) efficiency (%) (mV)
in Section 2.3. According to Fig. 7, the response surface model
revealed the optimized of PAC/PA and AF/PA as well as the 1 34.55635 1.25 96.512 −5.545
dominant in the coagulation processes. In the PAC/PA system, 2 19 1.25 96.124 −13.9
3 19 1.25 96.512 −14.5
4 19 1.25 97.481 −9.85
5 19 0.18934 95.155 −12.95
Table 4 – Levels of removal efficiency test with aluminum
6 19 1.25 97.384 −14.65
coagulant combined with PA for CCD design.
7 30 0.5 97.287 −6.245
Argument Level 8 19 2.31066 96.221 −14.7
9 8 2 65.019 −16.5
−α −1 0 1 α
10 3.443651 1.25 1.066 −18.5
Dosage of coagulant (mg/L) 3.4436 8 19 30 34.5565 11 30 2 98.062 −5.58
Dosage of PA(mg/L) 0.1893 0.5 1.25 2 2.3106 12 8 0.5 70.736 −16.55
102 J O U RN A L OF E N V I RO N ME N TA L S CIE N CE S 7 4 (2 0 1 8) 9 5– 1 0 6

Table 7 – Results of variance analysis for PAC combined with PA.

Sum of Mean F p-Value

Source squares df Square value Prob > F

Model 15,301.01 5 3060.201 47.47364 < 0.0001 significant

A-PAC 11,126.93 1 11,126.93 172.6148 < 0.0001
B-PA 2.521166 1 2.521166 0.039111 0.8498
A*B 0.206116 1 0.206116 0.003198 0.9567
A2 4165.946 1 4165.946 64.62733 0.0002
B2 113.0338 1 113.0338 1.753521 0.2336
Residual 386.7664 6 64.46106
Lack of fit 384.787 3 128.2623 194.3976 0.0006 Significant
Pure error 1.979381 3 0.659794
Cor total 15,687.77 11

had better color removal efficiency, but PA showed an obviously, and the dimension of the flocs could exceed
inconspicuous separate effect in the AF/PA system. 800 μm. PA, which is highlighted in blue, showed a large
The addition of PA did not improve coagulation efficiency, branched pattern composed of cubic units, and PA could
which was different from previous research showing that the easily be distinguished from the small branch-like AF flocs
coagulation efficiency was increased significantly when PA and the dye pollutant, with nubby appearance and vague
was used with aluminum sulfate (Guo et al., 2015). This was edges. Based on Fig. 9c and d, the floc structure pattern
because different coagulants were used in the two studies. changed a great deal when PA combined with small AF flocs to
The combined efficiency between simple polymeric alumi- form larger flocs when PA was added in the system. Although
num (Al2(SO4)3) and PA was much better than the interaction the assisting role of PA was proven by the SEM images, the
between complex polymeric aluminum (PAC) and PA. The optimum combination ratio for AF/PA formed flocs needed to be
zeta potential results in Fig. 7 show that the AF/PA system was confirmed. Therefore, variance analysis was an indispensable
closer to the isoelectric point than PAC/PA, which indicated tool for analyzing the interaction between the coagulant and
that the charge neutralization ability of AF was better than coagulant aid from the macroscopic viewpoint.
that of PAC. Based on the experimental design, PA was added To investigate the changes in chemical species during the
in the same dosage range when it was combined with PAC or coagulation process, FT-IR spectroscopy was used to measure
AF, therefore, any charge influence due to PA dosage can be the flocs in raw wastewater, those for PAC added alone, those
ignored, and the zeta potential differences between PAC/PA AF added alone, those in PAC/PA, and flocs in AF/PA. As
and AF/PA totally resulted from the charge neutralization shown in Fig. 10a, compared with the raw wastewater flocs, the
ability of the coagulants. Furthermore (Guo et al., 2015), spectra for PAC or PAC/PA flocs showed the disappearance of
the flocculating effect of PA was dependent on the UV254 many peaks in the range 700–1600 cm−1, which are considered
and DOC (dissolved organic carbon) removal efficiencies. The to be related to the meta-substitution and para-substitution in
improvement due to PA was shown clearly in the DOC the benzenoid structure of the reactive blue dye molecule.
removal efficiency (from 42% to 59%), but in the UV254 removal When PAC or PAC/PA was added into the system, all of the
efficiency, the removal efficiency only increased by 4%, peaks (910, 743 cm−1) in raw wastewater were replaced by a
which was a very slight advance. In this research, the dye strong peak at 805 cm−1, which was indicative of 1,2,3,4,5
removal efficiency was expressed as UV608, which might substitution in the benzene ring, and forcefully proved that
be another reason for the apparently insignificant effect of the substitution reaction occurred in the benzene ring. Accord-
PA addition. Besides, the DOC removal efficiency is an ing to Fig. 10b, when AF or AF/PA was added in dye wastewater
unnecessary index in dye wastewater treatment, and UV608 treatment, the same substitution took place as well. When PAC
is sufficient to represent the color removal efficiency. However,
in water supply treatment studies, such as that of Guo et al.
(2015), DOC removal efficiency is an indispensable index for Table 8 – Results of variance analysis for AF combined
with PA.
representing the heterogeneous organic matter in natural
water. Sum of Mean F p-Value

Source squares df square value Prob > F

2.3. The effect of PA addition on floc properties
Model 7944.276 5 1588.855 10.15243 0.0068 significant
A-AF 4732.43 1 4732.43 30.23917 0.0015
The finding of insignificant removal efficiency improvement
B- PA 1.474429 1 1.474429 0.009421 0.9258
by PA suggested that UV608 might not express the coagulant A*B 10.53652 1 10.53652 0.067326 0.8039
aid assistance completely. Therefore, SEM was selected to A2 2933.341 1 2933.341 18.7434 0.0049
examine the interaction between coagulant and PA through B2 26.65383 1 26.65383 0.170312 0.6942
microscopic images. As shown in Fig. 9a, the dimension of Residual 939 6 156.5
flocs was usually no greater than 50 μm when AF was added Lack of fit 937.6779 3 312.5593 709.2408 < 0.0001 significant
Pure error 1.322087 3 0.440696
alone, and the flocs exhibited a branch-like structure. When
Cor total 8883.276 11
PA was added in the system (Fig. 9b), the floc size increased
 J O U RN A L OF E N V I RO N ME N TA L S CI EN CE S 7 4 (2 0 1 8 ) 9 5– 1 0 6 103

Fig. 7 – Response surface for removal efficiency of aluminum coagulant combined with PA: PAC/PA (a), AF/PA (b). Response
surface for zeta potential of aluminum coagulant combined with PA: PAC/PA (c), AF/PA (d).

was added into the system, the peak at 3400 cm−1 became concluded that PAC bridged by means of hydrogen bonds.
broader than that of raw water. This phenomenon suggested Moreover, new peaks appeared at 2410, 1950, 805 cm−1, which
that the quantity of hydrogen bonds was increased and were the characteristic peaks for δ _CH, \C_C\ and δ _CH.
This revealed that alkene was formed in the coagulation
process. However, compared with the AF system, the flocs of
the AF/PA system did not show obvious differences in the FT-IR
spectra, even though the interaction of AF and PA was better
than that between PAC and PA. One explanation was that the
interaction between AF and PA was not dominated by chemical
bonds but by physical absorption. Besides the influence of
physical absorption on the coagulation ability of AF/PA,
some changes in the AF floc spectrum might indicate that the
pattern of connection of AF with the pollutant was different
that of PAC. In addition to the \COOH group of AF (peaks
at 3060, 3400 and 1640 cm−1), a peak for the newly formed
chemical matters attributable to C_C_O was found at
2400 cm−1, which indicated that AF captured the pollutant
by means of C_C_O bonds rather than δ _CH, \C_C\ and
δ _CH like PAC.
According to Fig. 10, the coagulation ability of PA was
questionable, in that none of the floc samples containing PA
showed PA's characteristic groups (such as \C`N, \NH3X−)
in the FT-IR spectrum. Therefore, the insignificant interaction
observed between the coagulant and PA might be attributed to
the poor purity of PA.

3. Conclusions

(1) AF was synthesized from aluminum hydroxide and

formic acid. FT-IR and XPS results found that COOH,
Al2O3-Al and O2-Al bonds were formed in the synthesis
Fig. 8 – The separate effects of PAC and PA in the PAC/PA process of AF, and the formation of Al2O3-Al and O2-Al
system (a), and the separate effects of AF and PA in the AF/PA in AF indicated that formic acid participated in the
system (b). polymerization of aluminum.
104 J O U RN A L OF E N V I RO N ME N TA L S CIE N CE S 7 4 (2 0 1 8) 9 5– 1 0 6

b
a PA
added

c

d

Fig. 9 – Image of flocs without coagulant aid used for SEM analysis (a), PA coagulation aid added (b); image of PA combined with
coagulant at PA molecule tip (c), at PA molecule trunk (d).

(2) Viscosity measurements revealed that the molecular range 1.6–8.0; however, the higher zeta potential of AF
size of AF was larger than that of PAC. Based on the than PAC implied that the formate groups in AF could
results of zeta potential measurements, AF showed a raise the zeta potential to improve the charge neutral-
hydrolysis mechanism similar to that of PAC in the pH ization ability in the pH range 8.0–13.4.

Fig. 10 – FT-IR spectra of flocs, with PAC as coagulant (a), AF as coagulant (b).
 J O U RN A L OF E N V I RO N ME N TA L S CI EN CE S 7 4 (2 0 1 8 ) 9 5– 1 0 6 105

(3) The hydrolysates of AF were determined by mass spec- Goncaf. Talu, V., 2004. formate ion decomposition in water under
troscopy measurements, which showed that the main UV irradiation at 253.7 nm. Environ. Sci. Technol. 38,
3984–3993.
hydrolysis product was Al13, while the main hydrolysate
Guo, B., Yu, H., Gao, B., Rong, H., Dong, H., Ma, D., et al., 2015.
product of PAC was Al9. The compositions of aluminum
Coagulation performance and floc characteristics of aluminum
salts were identified by XRD phase measurements, which sulfate with cationic polyamidine as coagulant aid for kaolin-
proved that AF consisted of aluminum formate (C3H3AlO6), humic acid treatment. Colloids Surf. A Physicochem. Eng. Asp.
aluminum formate hydrate (C3H3AlO6·3H2O) and alumi- 481, 476–484.
num hydrogen formate (C3H3AlO6·2H2O2). Guo, B., Yu, H., Gao, B., Zhang, S., Yue, Q., Xu, X., 2017. Novel
(4) The jar test results, as analyzed by the response surface cationic polyamidine: synthesis, characterization, and sludge
dewatering performance. J. Environ. Sci. 51, 305–314.
model, showed that the optimized dosage of AF/PA
Hellstén, P., Salminen, J., Jørgensen, K., Nystén, T., 2005. Use of
(when the color removal efficiency reached 100%) was formate in road winter deicing can reduce groundwater
18.91/0.71 mg/L, and the optimized dosage of PAC/PA deterioration. Environ. Sci. Technol. 39, 5095–5100.
was 21.19/0.91 mg/L. Hobbs, D.S.D.W.F., 1980. Physical and enzymatic properties of
(5) The interaction between coagulants and PA was proved by myosin from porcine brain. Biophys. Soc. 32, 705–718.
SEM images, which showed that the flocs became larger Ko, Y.G., Kim, C.J., Cho, Y.H., Chung, K.H., Kang, M.J., 2017.
Combustion/absorption process for the separation of 14C and
when PA was added. FT-IR spectra indicated that AF
3H in radwastes released from nuclear power plants and their
captured the pollutant by means of C_C_O bonds,
analysis. J. Hazard. Mater. 331, 13–20.
while PAC captured the pollutant by δ _CH, \C_C\ and Lee, W., Westerhoff, P., 2006. Dissolved organic nitrogen removal
δ _CH. during water treatment by aluminum sulfate and cationic
polymer coagulation. Water Res. 40, 3767–3774.
Liang, C.-Z., Sun, S.-P., Li, F.-Y., Ong, Y.-K., Chung, T.-S., 2014.
Treatment of highly concentrated wastewater containing
Acknowledgments
multiple synthetic dyes by a combined process of coagulation/
flocculation and nanofiltration. J. Membr. Sci. 469, 306–315.
This work was supported by the Tai Shan Scholar Foundation Malachova, K., Rybkova, Z., Sezimova, H., Cerven, J., Novotny, C.,
(No. ts201511003). 2013. Biodegradation and detoxification potential of rotating
biological contactor (RBC) with Irpex lacteus for remediation of
dye-containing wastewater. Water Res. 47, 7143–7148.
Appendix A. Supplementary data Mena, J.B., Ubices de Moraes, A.A., Benito, Y.R., Ribatski, G., Parise,
J.A.R., 2013. Extrapolation of Al2O3-water nanofluid viscosity for
temperatures and volume concentrations beyond the range of
Supplementary data to this article can be found online at
validity of existing correlations. Appl. Therm. Eng. 51, 1092–1097.
https://doi.org/10.1016/j.jes.2018.02.013. Mikola, M., Tanskanen, J., 2015. Preparation and coagulation
performance of solid aluminium formate. J. Water Process Eng.
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