1. Introduction
The wine industry is known to consume large volumes of fresh water, subsequently generating substantial amounts of wastewater and solid waste during production processes [
1]. This waste stream is often characterized by high concentrations of both organic and inorganic contaminants, which, if left untreated, may have negative impacts on the environment [
2].
Wine waste consists of a matrix of solid and liquid components. The solid components in wine wastes are generated during processes such as destemming, pressing, filtration, and settling. The solid waste is composed of skins, stems, excess grape pulp, seeds, stalks, and yeast cells that are generated during the process of fermentation [
3]. In relation to percentage composition, it consists of 7.5% grape stems, up to 45% grape pomace, and approximately 6% grape seeds [
4]. The liquid component, i.e., winery wastewater, on the other hand, is generated during the cleaning of barrels and tanks, washing of transfer lines and floors, wine extraction, as well as numerous other operations in filtration units and water drains [
5].
For every ton of grapes processed, wineries typically produce 3–5 cubic meters of wastewater [
6]. To contextualize this, the South African wine sector processed 1.2 million tons of grapes in total during the 2022 harvest season [
7]. As a result, the total volume of wastewater generated in this specific vintage season is estimated at approximately between 3.6 and 6 million cubic meters [
8]. Comparatively, the Australian wine grape crush for the 2022 harvest season was 1.7 million metric tons, implying that 5–10 million liters of wastewater was generated [
9]. An estimated 10.5 to 17.5 million cubic meters of wastewater was produced during the vintage season in 2022 as a result of the joint processing of 3.6 million tons of grapes by the California wine production business in the United States [
10].
The generation of these extensive quantities of wastewater is a cause for concern considering the world’s ongoing population growth and scarce water resources, which contribute to the challenge of limited access to clean fresh water [
11,
12]. The volume of winery wastewater produced poses additional sustainability-related difficulties in terms of environmentally sustainable discharge and reuse. This is made worse by the variable consistency and quality of wastewater from wineries, which fluctuates seasonally and typically contains chemical compounds that are harmful to the environment. As such, ensuring that appropriate treatment and disposal are consistently carried out becomes an essential objective for wineries [
13].
Winery wastewaters are notorious for their acidic pH, which is linked to the presence of various organic acids [
14,
15]. The electrical conductivity (EC) of winery wastewater may reach values up to 6.15 mS/cm [
16]. Nutrients in winery wastewater have caused high reported levels of total nitrogen (TN) and total phosphorous (TP) at 640 mg/L and 657 mg/L, respectively [
17,
18]. Chemical oxygen demand (COD) values routinely seen in winery wastewater generally fall within the range of 300 mg/L to the possibility of reaching values of up to 300,000 mg/L [
19,
20,
21].
There are serious and diverse environmental consequences linked to the unsafe discharge of wastewater from wineries into the environment [
15]. These include the release of foul odors mainly due to the high organic content of the wastewater, the degradation of soil quality, damage to vegetation as a result of wastewater disposal techniques, and overall pollution of water bodies [
22]. Based on these adverse environmental effects, wineries are requested to treat their wastewater to regulated standards before being discharged into the environment.
Coagulation and flocculation have, to date, been the staple processes during water and wastewater treatment [
23,
24,
25]. Generally, colloidal particles present in wastewater are negatively charged. The presence of these negative charges produces repulsion forces within the medium, hence decreasing the tendency of particles to aggregate, form floccules (flocs), and enhance sedimentation and flotation techniques. There have been extensive reports and literature studies related to conventional and emerging winery wastewater treatment options [
20,
26,
27,
28,
29]. However, many of these technologies are more applicable to treat wastewater from medium- to large-scale wineries rather than those from the many small wineries. A relatively new and emerging treatment option involves the use of hydrodynamic shear mixing with flotation [
30].
Hydrodynamic shear mixing has been previously used during emulsion processing as well as for the possessing of tight stable emulsions in petroleum wastewater treatment [
31,
32]. The basic principle of this technology involves the intentional destabilization of colloidal suspensions. This destabilization is achieved by subjecting the suspension to shear flow through mechanical agitation. The primary objective of this process is to facilitate the aggregation of micron-sized solid particles, resulting in the formation of larger flocs, which are more effectively separated from the liquid phase [
33].
The aggregation of colloidal particles is facilitated by shear flow through two primary mechanisms. In the case of kinetically stabilized colloidal suspensions exhibiting a sufficiently high energy barrier that prevents aggregation, it is possible for the convective energy (process of thermal energy exchange in fluids via the motion of matter within them) transmitted by the fluid to facilitate the particles to overcome the repulsive barrier and undergo aggregation. In the second situation, when dealing with totally destabilized suspensions, the rate of collisions is solely determined by the strength of the flow field. This leads to a significant acceleration of the aggregation kinetics in comparison to a purely diffusive mechanism [
34].
High shear mixers (HSMs) are considered to be an innovative and appealing form of process intensification equipment [
35]. These mixers show great potential with regard to enhancing the liquid–liquid extraction process inside solid–liquid–liquid systems. However, there is a scarcity of literature reporting on this particular aspect.
High shear mixers, much like flotation devices, have mostly been used in emulsion and mineral processing [
33,
36,
37,
38]. However, their potential to serve as an alternative treatment method for winery wastewater is yet to be proven. The potential of this technology to alter particle size as well as surface charges of colloidal particles needs to be explored in further detail, specifically in a practical sense.
This study focused on the key parameters of turbidity, total suspended solids (TSS), and particulate chemical oxygen demand (COD) in relation to the efficiency of winery wastewater treatment utilizing a hybrid shear enhanced flotation separation (SEFS) pilot plant. Due to the complexity of the treatment system (a nonsymmetrical system), which consists of a multiphase medium, the shear rate/speed in the rotor stator mixer configuration is an intricate parameter to quantify. As such, the terms shear rate/speed used throughout this paper have been simplified and quantified using revolutions per minute (rpm).
2. Materials and Methods
2.1. Untreated Winery Wastewater Collection
The winery wastewater used in this study was collected directly from a winery situated in the West Coast region of South Africa during the vintage period in April 2023. This untreated wastewater was used as feed water for batch experiments. The inherent wastewater treatment process at the winery involves the gravitational transfer of wastewater from the cellar, passing through a 2 mm screen grid. This grid separates a large portion of the solid substances, which is composed of a variety of substances including skins, seeds, stems, residual pulp, fragments of stalks, and yeast cells. The initial untreated wastewater for the pilot plant experiments was obtained from the waste stream, below the 2 mm screen grid, and transferred into a sequence of intermediate bulk containers (IBCs) using a Pedrollo RX2/20 submersible pump. The IBCs were relocated to the pilot plant facility located at the University of the Western Cape, Bellville, South Africa.
2.2. Alkalization Study
The experimental investigations for alkalization studies were carried out in 6 × 1000 L IBCs under standard ambient conditions of pressure and temperature. A lime slurry solution was prepared by mixing 10 kg of hydrated lime ((CaOH)2) sourced from Cape Lime (Pty) Ltd. in Vredendal, South Africa, with 100 L of tap water. The pH of the untreated effluent, initially at pH 4, was adjusted to a pH of 9 by adding 9% w/w of lime slurry to an initial starting volume of 800 L winery wastewater.
2.3. Pilot Plant P&ID
A pilot plant system was designed utilizing a conventional DAF treatment unit with the integration of a hydrodynamic shear mixer to treat winery wastewater at a rate of 5 L/min. The piping and instrumentation diagram (P&ID) of the pilot plant treatment system is illustrated in
Figure 1.
The pilot plant system consisted of intermediate bulk containers (IBC) flocculation tanks, a stainless-steel flotation tank, a recycle tank, an excess bubble release vessel, a microbubble generation pump, chemical dosing vessels, chemical dosing pumps, a needle valve (NV), gate valve (GV), shut off valve (SV), water level adjustor, flow meters (Fl), and ball valves (BV). The objective of the system is to study the extent to which organic and inorganic pollutants in winery wastewater can be removed utilizing hydrodynamic shear, coagulation, flocculation, and dissolved air flotation.
During experimental tests, the preconditioned winery wastewater (pH adjusted with lime slurry) was introduced and circulated through the unit until the pressure at PG-2 was stabilized at 2.5 bar. At this point, only BV-1 and BV-12 were open. After reaching this steady state, various processes and parameters were investigated, which included conventional dissolved air flotation treatment,) where coagulation (BV-2), flocculation (BV-4), and microbubbles (BV-8 inlet, and BV-11 outlet (as indicated by the green line)) and needle valve (NV-1) is opened. A hydrodynamic shear mixing unit was added (pink line) where the wastewater can be exposed to excessive mechanical agitation by way of shear. This is achieved by opening BV-13 and BV-16. The system was designed so that each individual subsystem could be tested as well as to test the synergistic effects of these subsystems.
The sampling points (SP) for each stage of treatment is as follows:
Coagulation (BV-3 and SP-1);
Flocculation (BV-5 and SP-2);
DAF-treated wastewater (BV-6 and SP-3);
Recycled water (BV-7 and SP-4);
Microbubble infused water (BV-10 and SP-5);
Sheared wastewater (BV-14 and SP-6).
2.4. Coagulation and Flocculation
In this investigation, the selection of treatment chemicals was based on the efficacy of aluminum-based polymeric coagulants and polyacrylamide flocculants in treating diverse types of wastewater [
25,
39,
40,
41,
42,
43]. The coagulant used during this study was a 1% (
w/
w) ACHD65, a composite of polydiallyldimethylammonium chloride (polydadmac) and aluminum chlorohydrate (ACH), having a specific gravity of 1.2. Polyacrylamide (PAM) granules served as the flocculant and were prepared as a 1% (
w/
w) solution using ultrapure deionized water obtained from a Milli-Q system manufactured by Millipore Co. in Billerica, MA, USA. The coagulant and flocculant chemicals were procured from Aqua Aero Vitae (Pty) Ltd., a company based in Cape Town, South Africa. This part of the study aimed to examine the impact of varying coagulant dosages on preconditioned wastewater samples with a pH level of 9. Zeta potential analysis was conducted to assess the ideal dosage of the coagulant based on the absolute surface charge reduction (i.e., destabilization) of the particles in the wastewater.
Coagulation and Flocculation Dosages
A typical jar test was conducted for chemical experiments. This method facilitates adjusting of pH as well as variations in coagulant and flocculant dosage to predict the effectiveness of a treatment plant operating on a larger scale. The experimental conditions related to coagulant and flocculant dosage have been described in a laboratory-scale study to treat winery wastewater [
44]. Briefly, 4
400 mL samples of preconditioned wastewater were subjected to various dosages of coagulant and flocculant in order to determine optimum dosages to be used in the pilot plant study. The jar tests were conducted in a FC4S VELP Scientific jar test unit (South Africa) using 76 × 25 mm flat paddle impellers at room temperature (23 ± 1.0 °C), as shown in
Figure 2.
In a typical coagulation experiment in the pilot plant, aliquots of coagulant were added directly to the preconditioned wastewater via BV-2. Coagulation experiments occurred with and without the addition of shear (BV-14, BV-15, and BV-16 closed) and microbubbles (BV-8, BV-11, and NV-1 closed). Samples were extracted from the sample points SP-1 and SP-4 and taken immediately for zeta potential analysis. Flocculation experiments followed coagulation where a predetermined concentration of PAM (aided by the jar tests) was injected into BV-4 in order to facilitate the aggregation of coagulated particles. Samples for flocculation experiments were extracted 15 min after recycling through SP-2 and SP-4 and analyzed for turbidity and total suspended solids.
2.5. High Shear Mixing
The shear unit was fabricated using steel sheets that were assembled to provide a sturdy external framework, accompanied by an internally rotating watertight unit, as illustrated in
Figure 3. The multilayered steel structure facilitates the creation of an extended shear gap of 1.3 mm between the rotor and stator, allowing for the passage of wastewater through an entry and exit point. Rotational speed (in rpm) of the mixer was quantified using a high-precision tachometer, DT2236E (Addendorff, Cape Town, South Africa). The shear mixer presented in
Figure 3 is currently part of a patent that has been filed and the exact details of the mixer will be presented in future work by the authors [
45].
2.6. Analytical Methods
2.6.1. pH and Electrical Conductivity
The pH and electrical conductivity (EC) measurements were performed with a portable multimeter (Hach, HQ40d, Randburg, South Africa) equipped with a conductivity probe. The determination of total dissolved solids (TDS) was accomplished by multiplying the electrical conductivity (EC) values with a conversion factor. The average conversion factor from EC measured in millisiemens per meter (mS/m) at a temperature of 25 °C to TDS measured in milligrams per liter (mg/L) has been documented as 6.5 [
46].
2.6.2. Turbidity
The turbidity of the samples was quantified using a Hach TL2350 turbidimeter equipped with a tungsten filament lamp, which was obtained from Agua Africa CC (Hach, South Africa). Turbidity measurements were conducted using the nephelometric method. The turbidity meter allowed for measurement values ranging from 0 to 10,000 nephelometric turbidity units (NTU).
2.6.3. Chemical Oxygen Demand
The term “chemical oxygen demand” refers to the quantification of the amount of oxygen required to oxidize the organic matter present in a sample using strong chemical oxidants such as potassium permanganate or potassium dichromate [
47]. This test is widely employed as an indicator of wastewater quality.
The COD of the samples was measured using a Thermo Fisher Scientific (Waltham, MA, USA) Orion Aquafast 3140 colorimeter in combination with an Orion COD165 Thermoreactor. The reagent vials used in this study were the Aquafast COD HR (High Range), 0–15,000 ppm Thermo Fisher Scientific (Waltham, MA, USA).
2.6.4. Zeta Potential
The measurement of zeta potential pertains to the surface charge of particles that are suspended in a medium. Its relevance in the context of wastewater applications lies in its capacity to quantify charge neutralization. The zeta potential is a quantification of the difference in electrical potential between the surface of a particle and the surrounding solution.
The examination of zeta potential (ZP) was performed using a Malvern Zetasizer NanoZS (Malvern Instruments Ltd., Worcestershire, UK) series, which employs the electrophoretic light scattering measurement technique [
48]. The investigation focused on analyzing the zeta potential measurements with respect to changes in coagulant dosage and application of various shear speeds. The laser employed in the Malvern Zetasizer Nano instrument was a 4 mW helium–neon (He-Ne) laser with a wavelength of 633 nm [
48]. A dip cell (Malvern Instruments Ltd., Worcestershire, UK) was utilized for the measurement of zeta potential. The dip cell was equipped with palladium electrodes (ZEN1002).
2.7. Total Suspended Solids
Total suspended solids (TSS) were determined according to ASTM D5907–18 [
49].
2.8. Bubble Size Analysis
An RS PRO USB Digital Microscope was used to capture images of bubbles produced during the treatment process. This microscope has a magnification ratio of 20
to 230
(optical zoom) and a capture resolution of 1920
1080. The examination of bubble size was performed using the ImageJ software package designed for Windows operating systems. ImageJ is opensource, Java-based image processing software; version 1.54d, (
https://imagej.net/ij), that is similar to NIH Image, a component of the National Institute of Health in the United States of America [
50].
2.9. Particle Size Analysis
The particle size of the wastewater was analyzed using a Microtrac S3500 Laser Diffraction Analyzer. Microtrac laser diffraction technology uses scattered light from multiple laser beams projected through a stream of particles. The amount and direction of light scattered by the particles are measured using an optical detector array and then analyzed using Microtrac Software (Microtrac FLEX 12.1.0.0).
4. Conclusions
This study focused on the design and application of a hybrid shear enhanced flotation separation (SEFS) treatment plant to process winery wastewater. Our study comprised the individual and synergistic effects of chemical additives and microbubbles, with and without shear. To our knowledge, this is the one of the first studies where hydrodynamic shear as a treatment component has been implemented during winery wastewater treatment. It has been shown that hydrodynamic shear as a component enhances overall treatment efficiency. The energy consumption for DAF treatment was 0.6 kWh/m3, whereas that of SEFS treatment was 1.1 kWh/m3. The nearly twofold increase in energy consumed was, however, justified by the total operational and energy costs to treat 1 m3 of wastewater. A 99.6% and 99.4% reduction in turbidity (a decrease from 849 NTU to 3 NTU) and TSS (a decrease from 2620 mg/L to 17 mg/L), respectively, was achieved through SEFS treatment in comparison to the 95.8% and 97.1% reduction in turbidity (a decrease from 849 NTU to 35 NTU) and TSS (2620 mg/L to 75 mg/L), respectively, achieved with conventional DAF. Chemical oxygen demand values were reduced by 66% (from 11,140 mg/L to 3800 mg/L) using the SEFS treatment system. Comparatively, a reduction of 51% for the COD was obtained using the conventional DAF treatment system (from 11,140 mg/L to 5490 mg/L). Not only was it shown that shear enhances treatment efficiency, but this technology also required 33% less coagulant and 37% less flocculant compared to conventional DAF treatment.
Solid waste analyses showed that the froth generated during the treatment process may be considered as a suitable source of fertilizer based on the nutrients contained therein. Before this solid waste can be considered for mixing with commercial fertilizer, the harmful/beneficial properties of the froth towards soil application should be thoroughly investigated.
The feasibility of SEFS technology to successfully treat agricultural wastewater has thus been shown and may also be applied to treat other wastewater types (e.g., pharmaceutical and municipal). This study showed a substantial reduction in COD; however, the remaining COD concentration in the wastewater is ascribed to the soluble fraction, which could not be removed using SEFS technology. The fraction of soluble COD is typically considered to be highly biodegradable due to the existence of easily biodegradable compounds such as simple sugars and disaccharides. Thus, future studies will include the further treatment of and reduction in soluble COD by means of biological treatment.