Electrooxidation (EO)
This is an advanced form of chemical oxidation technique which involves the generation of the oxidants that oxidize the pollutants through the application of electric current
[40]. The EO process is sometimes considered as part of the AOPs from a broad perspective but only the oxidation process occurs on the surface of the anode electrode as opposed to direct oxidation in the latter
[66]. The efficiency of the EO technique is affected by operating conditions such as the current density and electrode activity as well as the pollutants’ diffusion rate
[40].
3.4.3. Advanced Oxidation Processes
Chemical oxidation techniques are a set of treatment processes which can be broadly classified into two types: conventional chemical treatments and advanced oxidation processes
[60]. Advanced oxidation processes are highly efficient techniques used in the treatment of different types of wastewater including petroleum industry wastewater, toxic effluents from pharmaceutical industry wastewaters, etc. In previous years, several works have been reported in the literature to examine the efficiency of these processes
[60]. Precisely, advanced oxidation processes (AOPs) are a category of chemical treatment methods that produce free hydroxyl radical groups with strong oxidant potential which are capable of degrading contaminants. The most commonly employed AOPs in the treatment of PRWW include Fenton and photo-Fenton oxidation reaction processes, electrochemical oxidation, ozonation processes (O
3), as well as heterogeneous photocatalytic oxidation
[60][66]. The AOPs are gaining more attention nowadays as they are environmentally friendly techniques with less generation of secondary by-products and have shown high treatment efficiencies in the removal of organic compounds even at low concentrations
[13]. The treatment capability is attributed to the strong hydroxyl radical (
−OH) which has strong reactivity towards organic compounds and colour degradation potential
[74]. Based on this, AOPs have been reported as an efficient treatment technology for the reduction of COD, odour, colour, and other specific pollutants as well as sludge treatment. It can also be used in integration with biological treatment processes as a non-selective integrated chemical oxidant with high efficiency in removing toxic organic compounds such as phenols.
Fenton-Oxidation
Generally, among the AOP techniques, the Fenton technology is found to be very attractive due to its simplicity, high performance, low cost as well and lack of toxicity of the Fenton reagents which are usually ferrous ion and hydrogen peroxide
[75]. The Fenton process (FP) is based on a redox reaction between a chemical mixture of hydrogen peroxide (H
2O
2) and ferric ions Fe
2+ which have a strong oxidizing potential in an acid medium. It is a technique which was founded by Henry John Horstman Fenton in 1894
[65]. The hydroxyl radical is capable of the degradation of toxic and non-biodegradable pollutants by direct or indirect anodic oxidation
[40]. The OH radicals are extremely strong reactive oxidizers with an oxidation potential of approximately, Eθ = 2.8 V and they are generally non-selective towards organic pollutants in wastewater
[75]. There are two types of Fenton reactions: the standard Fenton reaction which is formed by a reaction between ferrous iron (Fe
+2) ions and hydrogen peroxide (H
2O
2), as well as the Fenton-like reaction which is formed by a reaction of (Fe
+3) ions and hydrogen peroxide
[76]. The Fenton reaction conducted under intense light such as UV or sunlight which generates more hydroxyl radicals is called the photo-Fenton reaction. Normally the ratio between the iron ions and the peroxide which is [Fe
2+]/[H
2O
2] is 1:2. However, the study reported by Quang et al.
[77] suggested a ratio of 1:5 for a greater rate of degradation. The Fenton-oxidation technique has been widely investigated in the treatment of different types of wastewater effluents including textiles
[77] and pharmaceuticals
[78]. However, the Fenton process’s general limitations include the problem of adding H
2O
2 and its lower utilization and mineralization efficiencies
[78]. The review reported by Elmobarak et al.
[60] also summarized that the major drawbacks of the Fenton and the photo-Fenton processes include their requirement for a very low pH value of usually less than 2 as well as the need for the elimination of the iron ions after the reaction process. Additionally, the potentiality of the
−OH radical degradation tends to reduce with a rise in the pH value. At a very low pH, there would be a creation of Fe (II) (H2O)
2+ which can react with the hydrogen peroxide (H
2O
2) leading to reduced generation of hydroxyl radicals.
Electro-Fenton Process
This is another novel oxidation technique which employs the electrochemical process and generation of TiO
2 oxidants by the Fenton-oxidation process. This technique has been studied for the removal of COD, BOD, TPH, phenols and other recalcitrant compounds which are not easily degraded in conventional treatment plants
[79]. For example, Fahim and Abbar
[80] have reported a study treating Al-Dewaniya PRWW in Iraq by the electro-Fenton process using porous graphite electrodes as anode and cathode materials. They used a tubular type of electrochemical reactor with a cylindrical cathode made from porous graphite and a concentric porous graphite rod which acts as an anode. At a current density of 25 A/cm
2, and operation time of 45 min with no addition of NaCl, the removal efficiency of COD was found to be 95.9% with an energy consumption of 8.921 kWh/kg per COD. The outcome of the experimental work has demonstrated the capability of the graphite–graphite electro-Fenton system as an effective technique in the removal of COD from petroleum wastewater. Similarly, Divyapriya and Nidheesh
[81] also reported from their review that the use of graphene-based electrodes in the electro-Fenton technique is usually considered to be a promising and cleaner method to produce the reactive oxygen species that can rapidly mineralize organic contaminants.
Photocatalysis
Photocatalysis is nowadays regarded as one of the most advanced, as well as environmentally friendly techniques for the total degradation of organic contaminants in various forms of wastewater
[82]. A photo-catalyst is often defined as a material such as titanium oxide (TiO
2) or transition metal oxides which can decompose harmful substances under the effect of sunlight containing UV rays
[83]. The process occurs by the excitation of pairs of electrons in the valence band by UV which causes them to absorb higher energy than their band gap energy which then causes the simultaneous production of a hole in the valence band (h
+) and an electron (e
−) in the conduction band. Furthermore, the (h
+) and (e
−) species will then react with oxygen or water molecules to produce peroxide or hydroxyl radicals which are capable of degrading or decomposing organic compounds
[13][83][84]. Depending on the specific characteristics of the semiconductor, the photolytic activity of photocatalysis is firstly initiated with the absorption of the energy in the form of photons which has an energy equal to or more than the band gap exhibited by the semiconductor such as the TiO
2 [85]. The process works on the basis that the hole created on the catalysts would in turn generate highly reactive hydroxyl radicals with high reduction–oxidation potentials such as •O
2−, H
2O
2, and •O
2 that can play an important role in the photocatalytic reaction mechanism
[86]. Photocatalysis has been employed as a more advanced practical and efficient process in the treatment of wastewater to degrade organic contaminants
[75][84][86]. In achieving this, pore volume, pore structure, crystalline sizes, light intensity as well as specific surface area are the important parameters which determine the excellent performance of photocatalysts.
Catalysts are the key requirement in the photocatalytic technique. A nano-catalyst usually possesses high surface area and density which gives it more photocatalytic activity and applicability in wastewater treatment
[87][88]. For example, a titanium dioxide (TiO
2)-based photocatalyst is the most widely used in wastewater treatment due to its high oxidizing ability of organic compounds, cost-effectiveness, nontoxicity, and environmental friendliness
[84][89][90]. Graphene, which is a carbon-based material has also been tested for photocatalysis applications and demonstrated high potential applicability for general pollutant removal. Dang et al.
[91] reported that the most important semiconductor catalyst widely employed for photocatalytic degradation of phenols includes: ZnO, CdS, TiO
2, GaP, ZnS and Fe
2O
3.
Properties of the Photocatalysts
Photocatalysts are usually employed either in the form of powders or thin films based on the requirements and scope of their application
[92]. The nano forms of photocatalysts are better at fast reaction rates than their corresponding bulk forms due to their small size and high surface area
[93]. However, using nanoparticles for wastewater treatment and pollutant degradation also has limitations related to their fast recombination losses and inadequate solar spectrum utilization
[94].
Metal Doping and Hybridization of Photocatalysts
Catalytic oxidation tends to increase with doping and hybridization modification processes, which increases the hydrophobicity and pollutant absorption strength of a photocatalyst
[86]. To increase or intensify the photocatalytic activity of a catalyst, doping techniques are applied to improve sensitivity to UV light as well as reduce the band gap and recombination rate
[84]. Besides improving photocatalytic activity, doping of catalysts also tends to reduce the amount of energy and wavelength required to be absorbed
[84][86]. Metals such as iron
[95], zinc
[96], silver
[97], platinum
[98], or non-metal elements such as nitrogen
[99] carbon and sulfur
[100] have been employed as metallic dopants to enhance photocatalytic performance. On the other hand, catalyst hybridization is another technique used to enhance the degradation potential of organic pollutants where photocatalysts are sometimes combined with absorbents such as graphite, SiO
2 and hydroxyapatite
[101].
Treatment of PRWW Using Photocatalysis
Due to the potential application using sunlight as a source of energy, this makes it an attractive technique for the degradation of organics from PRWW
[87]. The degradation of organic contaminants from PRWW by photocatalysis has been widely investigated using various forms of photocatalyst under varying conditions. Ghasemi et al.
[102] reported the treatment of PRWW by photocatalytic degradation using the TiO
2/Fe-ZSM-5 photocatalyst with as-synthesized Fe-ZSM-5 zeolite produced via sol–gel method with a specific surface area of 304.6 m
2/g and 29.28% loaded TiO
2. About 80% COD removal was achieved at a pH level of 4, photocatalyst concentration of 2.1 g/L, and 45 °C UV exposure temperature through 240 min. Although high COD removal efficiency was achieved, the synthesis of ZSM-5 zeolite catalyst is associated with a high production cost via complex processes influenced by the effect of time and temperature
[103].
Photocatalytic efficiencies of TiO
2 and zeolite for the removal of COD and SO
2− from PRWW were compared using a photocatalytic system by Tetteh et al.
[104]. The operating conditions of the system include a catalyst dosage of 0.5–1.5 g/L, a mixing rate of 30–90 rpm and an 18 W UV light. After a reaction time of 15–45 min, the results show almost the same efficiency of 92% for zeolite and 91% for TiO
2. Similarly, oil removal efficiency by photocatalysis has been examined by Mohammed et al.
[105] using a ZnO photocatalyst under a solar light to determine the effects of dosage, pH and initial oil concentration. The outcome of the experiment shows 75% oil reduction, and the optimum catalyst concentration was found with a 3 g/L dosage of ZnO and a pH of 10. The oil degradation rate decreased with increasing oil concentration which might be due to an increased level of turbidity because of the oil suspension which in turn decreased the permeation of the solar light intensity.
3.4.4. Combined H2O2/UV Advanced Oxidation Processes
The use of hydrogen peroxide as an oxidant in combination with potential sources of photon energy which can generate HO
− radicals has been reported to be more successful in providing the hydroxyl radical that can degrade organic pollutants
[80]. Using UV radiation of wavelengths >300 nm, H
2O
2 can decompose and generate HO
− radicals
[60]. Different researchers have reported that the degradation of pollutants by H
2O
2 continues steadily up to its highest efficiency after which it starts to decrease. This sudden decrease has been proven to be a result of the generating hydroxyl radicals which start to react with the additional H
2O
2 [106]. However, different advantages can be mentioned for the application of the H
2O
2/UV oxidation process, for example, there is no requirement for the removal of the hydroxyl radical after the treatment process and it is completely soluble in water
[107].
3.5. Integrated Treatment Processes (ITP)
It can be noted that most conventional and advanced treatment techniques have specific limitations in terms of their efficiency and are sometimes associated with various demerits for the treatment of PRWW. Based on this there is always a key interest in developing a novel procedure that overcomes limitations such as the operational costs, treatment efficiency, and generation of secondary pollutants. These challenges can sometimes be addressed through an integrated or combined treatment process which can yield a better benefit. For example, the combination of AOP techniques integrated with conventional methods used for the treatment of different contaminated industrial wastewater has been confirmed to be more efficient. However, as indicated in
Figure 8 the development of an integrated treatment process requires a good understanding of the PRWW characteristics, cost determination, as well as the requirements of environmental policies
[60].
Figure 8. The basic considerations in the selection of an appropriate treatment technique.
In most cases, the development of an integrated treatment process is initiated from a combination of two or more conventional and advanced methods. Hence, the configurations of such a combination can be a two-step, three-step or even multiple-treatment process. This might comprise at least one conventional and one advanced, two conventional and one advanced, or even two advanced processes. For example, an advanced oxidation process integrated with biological or other treatment techniques increases the efficiency of degradation as well as the separation of the contaminants. Based on this, the biological processes can provide the needed decomposition of the residual oil and degradation etc.
[108]. On the other hand, the integration of biological methods with membrane-based AOP techniques was also found to be an efficient process for the treatment of PRWW. However, in the development of a biological and chemical integrated process, the determination of the individual biological activity and chemical oxidation efficiencies is important for finding the optimal operating conditions for the combined process. This involves a profound knowledge of the operational conditions for both the biological and chemical processes.
4. Conclusions
Environmental pollution due to oil refinery wastewater is a global phenomenon that attracts serious attention due to its harmful effects on the ecosystem. Nowadays, the need to meet the maximum concentration limit for PRWW is usually challenging for petroleum refinery industries. This is because petroleum wastewater has a dynamic, complex nature. Hence, various conventional and advanced treatment techniques such as adsorption, membrane filtration, chemical precipitation, and biological systems have been designed to address this challenge over the years. While some already established techniques are mature in their applications, others are associated with various challenges and limitations. The appropriate treatment technology selection mostly depends on the oily wastewater composition, operational costs, efficiency, and environmental impacts. However, as the nature of PRWW is mainly in the form of oil-in-water emulsions, a correct understanding of their physical and chemical composition is needed. Although membrane treatment techniques have demonstrated an efficient removal capacity for organic and inorganic contaminants, they are associated with fouling and the problem of salt build-in bioreactors. New and advanced treatment techniques such as adsorption with modified non-conventional adsorbents, photocatalysis, and other advanced oxidation processes have been reported with significant efficiency in refinery wastewater treatment. For example, photocatalysis treatment techniques are effective in reducing COD, oil and grease concentrations, and phenol degradation. The alternative use of solar power as an energy source also makes it a considerable treatment option. Meanwhile, adsorption techniques using non-conventional adsorbents such as hydrogel were also effective in treating synthetic petroleum wastewater. They are less costly as well as environmentally friendly in their application.