- Journal Details
- Format
- Journal
- eISSN
- 2544-4646
- First Published
- 04 Mar 1952
- Publication timeframe
- 4 times per year
- Languages
- English
Coal is one of the most important global energy resources and comprises the majority of China’s energy economy. However, coal mining and its use in energy applications have resulted in considerable ecological issues. Coal washing wastewater is the tailwater of wet coal washing in coal processing, which contains large amounts of silt and slime with a typical characteristic of dark black color (Kirk et al. 2003; Yan et al. 2012). The vicinity of the coal mine has caused serious environmental pollution, and coal washing wastewater is one of the main sources of pollution in the coal industry, and increases public environmental attention (Lemly 2018). Coal washing wastewater is a colloidal suspension that can remain stable for months. It contains small particles that do not undergo gravitational sedimentation and their surface negative charge prevents them from colliding with each other and forming bigger flocs, which can settle easily (Yan et al. 2012; Thiruvenkatachari et al. 2016; Kapse et al. 2017). Consequently, the recycling and reuse of post-treatment effluent can be an efficient approach to reduce the volume of effluent that is discharged into environments. China is one of the largest coal-producing countries in the world (IEA 2018), and is facing with the intractable problem of remediating coal washing wastewaters produced daily. The removal of suspended solids (SS) from wastewaters could relieve environmental burdens from discharge, and also help to increase coal production (Duong et al. 2000). Coal washing wastewaters require massive amounts of flocculants (Wang et al. 2017), thus the efficient and environmentally friendly bioflocculants would be of significant advantage.
Several methods have been used to treat such wastewaters, including ion exchange, filtration, flotation, flocculation, and solvent extraction (Geremias et al. 2003). Among these technologies, flocculation that includes coagulation/flocculation, and direct flocculation is an effective and easily applied method in the removal of insoluble particles from wastewaters (Bolto and Gregory 2007; Teh et al. 2016). Flocculation removes organic compounds along with suspended solids and also decolorizes waste streams. In particular, coagulation/flocculation with poly aluminum chloride (PAC) and anionic polyacrylamide (A-PAM) can be used to reduce significantly the abundance of suspended solids of coal washing wastewaters. However, the dosages and concentrations of coagulants used are proportional to the waste material levels in the wastewaters (Duong et al. 2000; Li et al. 2010; Luo et al. 2011; Wang et al. 2017). Furthermore, conventional coagulants including PAM and PAC are expensive, corrosive, and biologically harmful. Specifically, PAM monomers (acrylamide) are strongly neurotoxic (Friedman 2003; Hariri et al. 2015) and would raise a significant danger to the environment and human health. Therefore, an effective, chemically non-invasive, and low-cost coagulant alternative is needed to meet the stringent environmental regulations expected for discharged effluent or solid waste qualities (Zeng et al. 2007; Luo et al. 2011).
The most of alternative flocculants are bioflocculants, which have attracted recent research and industry interest due to their high flocculation capacities, eco-friendly properties, and biodegradability. Moreover, some of these new flocculants can be produced from biological or agro-industrial wastes (Shahadat et al. 2017). Over 100 species of bioflocculant-producing microorganisms have been described and investigated with respect to their flocculation performance in different wastewater types, for example, the bioflocculant IH-7 produced by
In our previous work, a novel bioflocculant-producing fungus strain
For purifying the bioflocculant, the culture broth was centrifuged at 6000 rpm for 10 min after seven days of incubation, then followed by the collection of the supernatant and was concentrated to one-third of the initial volume at 50°C. Threefold volumes of cold ethanol (at 4°C) were poured into and kept for 24 h at 4°C. After centrifugation at 6000 rpm for 15 min again, the precipitate was washed with ethanol, freeze-dried, and assigned as IC-1 (Fig. 1A, 1B).
Fig. 1.
Purified IC-1 from
The total sugar content of IC-1 was determined according to the phenol sulfuric acid method using glucose as standard, and the total protein content was determined by the Bradford method with bovine serum albumin as the standard (Guo et al. 2014). The neutral sugar and the galacturonic acid content of IC-1 were measured by an anthrone reaction and the carbazole-sulphuric reaction, respectively.
The flocculating efficiency was investigated by the following procedure. Briefly, 1 g l-1 of IC-1 (Fig. 1B) or APAM was prepared and then added into 50 ml coal washing wastewaters at a different dosage. The mixture was stirred slowly for few minutes by employing a magnetic stirrer at 60 rpm and was stood for a short time according to the optimized mixing and sedimentation times. Then, the optical density (OD) of the supernatant at 550 nm was measured using a spectrophotometer (GENESYS 10 UV, Thermo Scientific, USA). The flocculating efficiency was then calculated using the following equation:
-where A550 and B550 were the OD550 (optical density at 550 nm) of the treated sample and the control sample supernatants, respectively. Control samples were the untreated coal washing wastewater. All experiments were conducted in triplicate.
Based on its main components, it could be assumed that IC-1 might be of high molecular weight anionic polysaccharide due to the presence of galacturonic acids, whose carboxyl groups would be probably dissociating around neutral pH. The molecular weight of these fungal polysaccharides was approximately estimated in the range of from 1.1 × 104 to 1.48 × 107 Da that is quite similar to the molecular weight of biopolymers from
Fig. 2.
The flocculating performance under various conditions. (A) Different dosage of IC-1; (B) Different mixing time; (C) Different sedimentation time; (D) Different dosage of CaCl2 as a coagulant. Error bars indicate standard deviation of triplicate experiments. Significant differences among different treatments are indicated by lowercase (
The mixing test was conducted by a magnetic stirrer and the effect of the mixing time was investigated. In Fig. 2B, the flocculating efficiency showed a slight downward trend with the increasing mixing time. But the sedimentation time led to little effect on the flocculation efficiency, as shown in Fig. 2C.
In addition, Ca2+ was the most favorable metal ion for the flocculation in kaolin suspensions (Li et al. 2017). Fig. 2D showed a similar effect like that for the flocculating efficiency in the treatment of coal washing wastewater. An additional 2% CaCl2 dosage enhanced rapidly flocculating efficiency up to 95.8%. However, only minor enhancements of flocculation were observed with higher CaCl2 dosages. As a result, the optimal CaCl2 dosage was estimated at 2%. Table I summarized the comparison of the flocculation performance of IC-1 with other bioflocculants for the coal wastewater, either under the condition with the additives or not. Nevertheless, it might be not assured that inorganic coagulants would be necessary for the bioflocculant, such as POS412 produced by
Flocculation performance of IC-1 compared with other microbial flocculants for the coal wastewater treatment.
| Bioflocculant | Origin | Maximum Flocculating Efficiency | Additives |
|---|---|---|---|
| IC-1 |
| 95.8% | 2% CaCl2 |
| POS412 |
| 96.53% (Xu et al. 2017) | |
| MBF-L918 |
| 95.51% (Liu et al. 2016) | |
| A bioflocculant |
| 95.76% (Yang et al. 2019) | 50 mg/l CTAB |
It was well known that the coal particle surface shows a strong negative charge (Yan et al. 2012; Xu et al. 2017). Few cations are commonly applied to neutralize the negative charges of cation-dependent bioflocculants and kaolin particles, thereby allowing increased adsorption of bioflocculant onto kaolin particles (Dermlim et al. 1999). Moreover, the charges and radius of the cations could affect the flocculating activity, and a bigger radius led to lager bonded particles which could be easily settled (Sousa et al. 1992). Our results showed that the flocculating activity of the bioflocculant was Ca2+-dependent, and the flocculating activity was about 95.8% at the CaCl2 dosage of 2%. This result was agreed with the report that many microbial flocculants were cation-dependent, such a bioflocculant from
Fig. 3.
The flocculating efficiency of IC-1 and APAM at different dosages. Error bars indicate standard deviation of triplicate experiments. Significant differences among different treatments are indicated by lowercase (
There must be an optimal dosage for the performance of the different bioflocculants in various conditions. The flocculating activity should be highest under optimal dosages, with decreasing activity at suboptimal dosages though. Specifically, flocculating efficiencies would suffer from too low the bioflocculant concentration at lower than optimal dosages. In addition, higher than optimal dosage would also inhibit activity. At suboptimal bioflocculant levels, bridging can not effectively occur. In contrast, the excessive addition of negatively charged bioflocculant would lead to competition and repulsion of negatively charged coal particles (Yan et al. 2012), thereby leading to poor settling (Gong et al. 2008). In this scenario, colloid particles are surrounded by abundant polymers in wastewaters and are stabilized due to the absence of bridging (Pu et al. 2014). Thus, the over-dosing of IC-1 impacts adversely flocculation.
The goal of treating coal washing wastewaters is to accelerate the particle settling rate and reduce wastewater contaminants. Therefore, the settling time is an important parameter that is used to evaluate the behavior of wastewater treatment. Figure 4 showed the settling time difference among the untreated sample, APAM-assisted, and IC-1-assisted flocculation. In the untreated samples, coal particles remained suspended after 10 min of sedimentation, whereas in the case of the APAM-assisted and IC-1-assisted treatment, coal particles were flocculated into flocs which settled easily (Fig. 4E). Remarkable changes happened after 1 min by adding APAM and IC-1. In Fig. 4A and Fig. 4C, a great number of flocs were formed in the APAM-assisted and IC-1-assisted treatment of coal washing wastewater and the flocs in APAM-assisted treatment were larger than that in IC-1-assisted treatment. Five minutes later, although the number of the flocs reduced greatly in the APAM-assisted and IC-1-assisted treatment of coal washing wastewater (Fig. 4B, 4D), the size of the flocs in the APAM-assisted treatment was still larger than that in IC-1-assisted treatment. It revealed that APAM may more easily accelerate the formation of flocs compared to IC-1.
Fig. 4.
The flocculating process after the dosage of IC-1 and APAM. The comparisons between: (A) CK and APAM-assisted samples after 1 min of sedimentation; (B) CK and APAM-assisted samples after 5 min of sedimentation; (C) CK and IC-1-assisted samples after 1 min of sedimentation; (D) CK and IC-1-assisted samples after 5 min of sedimentation; and (E) the comparison among CK, IC-1-assisted, and APAM-assisted samples after 10 min of sedimentation. CK means a control check, i.e., the raw sample without adding any flocculant.
Figure 5 shows the microscopic images of the fine particles in the samples treated by IC-1 and APAM. As shown in Fig. 5A and Fig. 5B, the fine particles in the untreated sample sediments were mostly scattered and kept suspended, which resulted in little change even after 10 min of sedimentation. However, the flocs in the treated samples were formed after adding APAM and IC-1, respectively in Fig. 5C and Fig. 5E, which implied that the addition of the flocculant may trigger the formation of large flocs during flocculating process. From Fig. 5D and Fig. 5F, the flocs in the IC-1-assisted sediments were more compact than that in the APAM-assisted sediments. It indicated that the sediments treated with IC-1 may be more stable than those treated with APAM. Polymer bridging and charge neutralization are two well-known mechanisms that contribute to flocculation (Li et al. 2017; Xu et al. 2017). The results described above revealed that polymer bridging could take place after adding IC-1, which might assist fine particles of coal to connect flocs together and form larger aggregates.
Fig. 5.
Microscopic images of the fine particles after addition of IC-1 and APAM. (A) CK (10 mm); (B) CK (10 μm); (C) IC-1 (10 mm); (D) IC-1 (10 μm); (E) APAM (10 mm); (F) APAM (10 μm). CK means a control check, i.e., the raw sample without adding any flocculant.
The estimated costs of APAM and IC-1 to treat 1 metric ton of coal washing wastewater at the same flocculating efficiency.
| Cost/t | Dosage/g m−3 | Cost per metric ton of wastewater | |
|---|---|---|---|
| APAM | US$ 2300 | 60 | US$ 0.13 |
| IC-1 a | US$ 2500 | 24 | US$ 0.06 |
The cost of IC-1 was estimated according to the market price of the culture substrate, and the maximum biopolymer yield is around 14.02 g per 100 ml culture substrate.
The focus of the present work aimed to investigate the performance of IC-1 in the treatment of wastewater, not like other studies that relied on bioflocculant behavior via kaolin suspensions. As it has been shown, the results of the present study inferred that IC-1 from
Like IC-1, other biodegradable bioflocculants have attracted the increasing scientific and technological consideration in wastewater treatment applications because they are harmless to human health and do not cause secondary pollution via the degradation of intermediate metabolites (Okaiyeto et al. 2014). As a traditional Chinese medicine,
In summary, IC-1 has shown to be an effective and alternative microbial flocculant for the coal washing wastewater treatment. The maximum flocculating efficiency was found to be 91.81% after the addition of IC-1 at the dosage of 24 mg l–1 and even up to 95.8% when assisted by 2% CaCl2. When compared to IC-1, the cost of the APAM application is relatively higher (around $0.13 t–1), almost two times as the cost of the IC-1 application. In light of the results, the utilization of IC-1 for the treatment of coal wastewater would be a useful, economical, and environmentally friendly alternative to conventional flocculants like APAM when the extra cost has to be involved in the post-treatment.
Fig. 1.
Fig. 2.
Fig. 3.
Fig. 4.
Fig. 5.
Flocculation performance of IC-1 compared with other microbial flocculants for the coal wastewater treatment.
| Bioflocculant | Origin | Maximum Flocculating Efficiency | Additives |
|---|---|---|---|
| IC-1 |
|
95.8% | 2% CaCl2 |
| POS412 |
|
96.53% ( |
|
| MBF-L918 |
|
95.51% ( |
|
| A bioflocculant |
|
95.76% ( |
50 mg/l CTAB |
The estimated costs of APAM and IC-1 to treat 1 metric ton of coal washing wastewater at the same flocculating efficiency.
| Cost/t | Dosage/g m−3 | Cost per metric ton of wastewater | |
|---|---|---|---|
| APAM | US$ 2300 | 60 | US$ 0.13 |
| IC-1
|
US$ 2500 | 24 | US$ 0.06 |