Due to the presence of environmental problems, it is urgent to improve the processes aimed at the processing and purification of hydrocarbon-containing wastes and wastewaters. The research presents the latest achievements in the development of nanostructured catalysts made from different materials that can be used to purify oil-polluted wastewaters (petroleum refinery wastewater, oilfield-produced water, sulfur-containing extracts from pre-oxidized crude oil and oil fractions, etc.) and eliminate components of hydrocarbon pollutants (polyaromatic hydrocarbons, phenols, etc.). The results of the analysis of possible combinations of chemical and biological catalysts for deeper and more effective solutions to the problems are discussed. The possibilities of highly efficient elimination of hydrocarbon pollutants as a result of the hybrid application of nanoparticles (graphene oxide, mesoporous silica, magnetic nanocatalysts, etc.) or catalytic nanocomposites for advanced oxidation processes and biocatalysts (enzymes, cells of bacteria, mycelial fungi, phototrophic microorganisms and natural or artificial microbial consortia) are analyzed.
NCs/NComs; Size (nm) [Reference] |
Pollutants | Reaction Conditions | Removal Efficiency (%) |
---|---|---|---|
Heterogeneous photocatalysis | |||
TiO2 (30 nm) [18] |
Phenol (300 ± 7 mg/L), soap oil and grease (SOG) (4000 ± 23 mg/L) in oil refinery wastewater | 8 g/L of catalyst, aeration flow rate of 1.225 L/min, 90 min | 76% of phenol and 88% of SOG |
TiO2 (44.3–48.0 nm) [19] |
Anthraquinone (0.5 mg/L) |
200 mg/L of catalyst, solar irradiation 100 mW/cm2, 240 min | 57% |
Haematite (α-Fe2O3) [20] | Petroleum refinery wastewater COD 1257 mg/L |
pH 7.5, 1.494 g/L of catalyst, H2O2/COD ratio of 1 mg/mg, UV-A lamp solar irradiation, 90 min |
90.85% of COD |
ZnO or NiO [13] | Anthracene (101.8 mg/L) |
pH 7.2, 55.6 mg/L of catalyst, emulsion solution—230 min, anthracene aqueous ethanol solution—280 min | 90% with ZnO and 87% with NiO for anthracene emulsion solution; 81% with ZnO and 86% with NiO for anthracene aqueous ethanol solution |
ZnO nanorods 2.11 ± 0.32 μm length and 96.26 ± 11.13 nm diameter [21] |
Phenol (10 mg/L) |
pH 5, visible light 1000 W/m2, 5 h |
84.3% |
ZnO/SiO2 with Palash leaves extract (3–35 nm) [22] |
Acenaphthylene (176 mg/L), COD (497 mg/L) in petrochemical wastewater | 1 g/L of catalyst, 30 °C, visible light, 4 h |
79% of Acenaphthylene, 70% of COD |
HS-CuS-HNCs Hierarchically structured CuS hollow nanocatalyst [12] |
Petroleum refinery wastewater (COD 380 mg/L) |
pH 7.6, 1 g/L of catalyst, 180 min, 10 cycles |
about 66% of COD |
TiO2@ZnHCF Titanium dioxide based zinc hexacyanoferrate framework nanocomposite (100 nm) [23] |
Tricyclic PAHs: acenaphthene, phenanthrene and fluorine (2 mg/L) |
Neutral pH, 15 mg/L of catalyst, sunlight, 6 h | 93–96% from water, 82–86% from soil, 81.63–85.43% from river sediment |
Fe3O4/Cu2O-Ag nanocomposite (5 nm) [24] | PAHs: naphthalene (5 mg/L), benzo(a)pyrene (5 mg/L), anthracene (5 mg/L) | 0.5 g/L of catalyst, visible light, 60–180 min | 80–90% |
MIL-101(Cr)/Fe3O4-SiO2 (35% of Fe3O4-SiO2) Superhydrophobic composite (400/80–120 nm) [14] |
Synthetic and real oilfield-produced water (TPH 170 mg/L, COD 550 mg/L) | pH 4, 0.5 g/L of catalyst, visible and UV light, 150 min | 97.7% and 99.2% of TPH, 95.17% and 96.6% of COD from real and synthetic OPW, respectively |
Fenton-like oxidation process | |||
Nanoscale zero-valent iron (nZVI), commercial (50 nm) [25] |
Water from oil and gas exploration site (15 different PAHs present in real water samples; Naphthalene (201.46 μg/L) and benzo(g,h,i) perylene (23.15 μg/L) |
pH 2.94, 4.35 g/L of nZVI, 1.60 g/L of H2O2, 199.90 min |
89.5% and 75.3% of PAHs and COD, respectively |
MgAl-LDH@Fe3O4 [26] | Concentrated liquor of gas field wastewater (refractory organic pollutants) | pH 5, heterogeneous electro-Fenton system, 4 h | 88.18% for COD |
Cl/S-codoped carbon nitride nanotube clusters (Cl/S-TCN) [27] | Oilfield-produced water | pH range 3–9, metal-free photo-Fenton, 10 mM H2O2 | 82.6% for COD |
Ozonation | |||
CuO/Activated carbon (250~350 nm) [28] |
Heavy oil refinery wastewater (oil 78 mg/L, COD 2950 mg/L) | pH 7.3, 5.0 g of catalyst, 90 mg/L of O3, 75 min |
94.2% of COD 89.7% of oil |
Sulfate radical-based oxidation | |||
OMS-2 Manganese oxide octahedral molecular sieve nanorods [29] |
PAH: phenanthrene (1.0 mg/L) in water and sewage | pH range 4–11, 0.1 g/L of catalyst, peroxomonosulfates 6 mmol/L, room temperature, 360 min, 3 cycles |
>99%, 68%, 82% and 79% from model wasterwater, tap water, Yellow river and Qinghai lake, respectively |
Hybrid chemical processes with nanocatalysts | |||
HS-CuS-HNCs Hierarchically structured CuS hollow nanocatalyst [12] |
Petroleum refinery wastewater (COD 380 mg/L) |
Heterogeneous photocatalysis/H2O2 pH 7.6, 1000 mg/L of catalyst, 3000 mg/L of H2O2, room temperature, solar-light, 2 h |
98% of COD |
M.MIL-100(Fe)@ZnO [30] | Phenol (5 mg/L), Biphenol A (5 mg/L), Atrazine (5 mg/L) |
Heterogeneous photocatalysis/H2O2 pH 2, 0.2 g/L of catalyst, 10 mM H2O2, room temperature, 2 h |
95% of Phenol, 95% of Biphenol A, 85% of Atrazine |
CuO/ZrO2 nanocomposite 40.32 nm [31] |
Marine diesel (100 mg/L) |
Heterogeneous photocatalysis/H2O2 0.5 g/L of catalyst, 400 °C, 0.3 g/L of H2O2, visible light, 6 h |
96.96% |
Cu-based perovskite oxides (La2CuO4) [32] | Petroleum refining wastewater (COD 3800 mg/L TOC 1259 mg/L) |
Wet air oxidation processes/H2O2 pH 7.5–8.0, 0.75 g/L of catalyst, 7 mL/L of 30% H2O2, 100 ℃, 0.5 h |
89.58% of COD, 87.38% of TOC |
Biocatalyst [Reference] | Pollutants | Conditions and Degradation Efficiency |
---|---|---|
Homogenous BCs | ||
Achromobacter xylosoxidans [33] | Pyrene 100 mg/L | pH 7–9, 37–40 °C, 0–2.5% NaCl, 15 days, 50% of of pyrene |
Halomonas shengliensis [34] | Pyrene 50 ppm | 25 °C, 10 g/L NaCl; 50% degradation |
Penicillium sp. [35] | Crude oil 1% (v/v) | 14 days, 30 °C; 57% degradation |
Chlorella vulgaris [36] | Oilfield-produced water (7 mg total hydrocarbons/L) and crude oil (32 mg total hydrocarbons/L) | 5 days, 20 °C; 36.8 ± 4.2 μmol photons/m2/s 28.5% degradation from oilfield-produced water; 34.3% degradation from crude oil |
Rhodocccus erythropolis or Pseudomonas stuzeri [37] | PAHs (332.2 mg/kg soil) |
Slurry Bioreactor, 28 °C, pH 8.2; 8 mg/L dissolved oxygen, 15 days, 70–80% degradation |
Brevibacillus brevis [38] | Naphthalene and pyrene (100 mg/L) |
pH 5.0, 25 °C, 18 days, 80% of naphthalene |
Proteus mirabilis [38] | pH 5.0, 25 °C, 18 days, 94% of naphthalene | |
Rhodococcus quinshengi [38] | pH 5.0, 37 °C, 18 days, biodegradation: 94% of naphthalene, 56% of pyrene |
|
R. ruber Ac-1513 D and R. erythropolis Ac-1514 D [39] |
Petroleum hydrocarbons 446.7–526.8 g/kg dry soil | Aerobic-anaerobic bioremediation method with 108 cells/mL; nitrate salt is used as electron acceptor on area 25 × 30 m2 3 times with a 3-week interval; 20–30 °C; 63 days; Degradation of saturated, aromatic and resin-asphaltene was 72.6%, 66.5% and 57.2%, respectively. |
R. ruber Ac-1513 D and R. erythropolis Ac-1514 D [40] |
Oil products 482 g/kg dry soil (48%) |
Hydrolysis of the bituminous crust by calcium hydroxide (2%) 3 times with a 3–4-day interval; bioremediation with Rhodococcus strains (106 cells/mL) was conducted 3 times with a 7-day interval; 20–30 °C, pH 7.8; 33 days for 26.4–48.2% degradation of oil pollution |
R. ruber Ac-1513 D and R. erythropolis Ac-1514 D [41] | Oil products 98 g/kg dry soil (9.8%) |
Anaerobic bioremediation, 109 cells/mL electron acceptor Ca(NO3)2; 1.25%, 28 °C, pH 7.8; 10 days; potential degradation of the oil pollution 90% for 90 days |
Extremophilic consortium: Ochrobactrum, Bacillus, Marinobacter, Pseudomonas, Martelella, Stenotrophomonas and Rhodococcus [42] | Low-molecular-weight (LMW) petroleum hydrocarbons (200 ppm) such as anthracene, phenanthrene, fluorene and naphthalene |
Soil, 8% salinity, pH 10, 60 °C, 8 days, 100% degradation efficiency |
High-molecular-weight (HMW) hydrocarbons such as pyrene (100 ppm), benzo(e)pyrene (20 ppm), benzo(k)fluoranthene (20 ppm) and benzo(a)pyrene (20 ppm) |
Soil, 8% salinity, pH 10, 60 °C, 8 days, 93%, 60%, 55% and 51% degradation |
|
Consortium: Campylobacter hominis, Bacillus cereus, Dyadobacter koreensis, Pseudomonas aeruginosa, Micrococcus luteus [43] | Bonny light crude oil | 2% (v/v) crude oil, 30 °C, 21 days 73% degradation |
Consortium of genus Pseudomonas, Methylobacillus, Nocardioides, Achromobacter, Methylophilaceae, Pseudoxanthomonas, Caulobacter [15] | The final concentration of total PAHs from coal and petroleum was 97.63 mg/ kg dry weight soil | 35 days, 25 °C, in soil; 75% PAHs |
Halophilic bacterial consortium [44] | PAHs | 12 days, pH 7.4, 40 g/L NaCl concentration low-molecular-weight (above 90% for phenanthrene and fluorene) and high-molecular-weight (69 ± 1.4 and 56 ± 1.8% at 50 and 100 mg/L of pyrene) polycyclic aromatic hydrocarbons (PAHs) |
Benthic diatom-associated bacteria [45] | 3 μg/L Benzo(a)pyrene and 265 μg/L fluoranthene | 7 days, 88% of fluoranthene, 79% of Benzo(a)pyrene |
Consortium: Aspergillus niger, Aspergillus sydowii, Fusarium lichenicola [46] |
101.7 mg/L PAHs in oilfield wastewater |
21 days, 85.2% degradation (with 100% naphthalene and chrysene) |
Consortium of Chlorella sp. and Rhodococcus wratislaviensis with preliminary adaptation [47] |
Mixture of 50 mg/L phenanthrene, 10 mg/L pyrene, 10 mg/L benzo[a]pyrene |
24 °C, 200 μmol photons/m2/s, 150 rpm, 21 days 100% degradation |
Nannochloropsis oculata or Isochrysis galbana with preliminary adaptation [48] |
Oilfield-produced water (270 mg oil/L) |
pH 7.2, 25 ± 1 °C, light photoperiod—18:6 (2000 lux); 66.5–68% degradation |
Immobilized BCs including self-immobilized systems (biofilms) | ||
Bacterial consortium immobilized in magnetic floating biochar gel beads [49] | Pyrene (20 mg/L), benzo(a)pyrene (10 mg/L), indeno(1,2,3-cd)pyrene (10 mg/L) |
Seawater, pH 8.1, 30 °C, 30‰ salinity, 16 days. Biodegradation: 89.8%, 66.9% and 78.2% of PYR, BAP and INP, respectively |
Biofilm and pellets of consortium (key functional genera: Rhodobacter, Citreibacter, and Roseovarius) [50] | Oilfield-produced water (6.38 ± 2.31 mg oil/L) |
multistage bio-contact oxidation reactor, pH 7.5–8.1, 45–50 °C, 44.07% oil degradation |
Microbial mats (cyanobacteria and bacteria) [51] | Oilfield-produced water (4.3 ± 1.0 mg of the C10 to C30 alkanes/g mats) |
28 days, 30 °C, 50 rpm, pH 8.5, 18 ppt salinity, with partially hydrolyzed polyacrylamide; 41–49% degradation |
Active sludge [52] | Synthetic produced water (255 mg oil/L) |
Aeration tank, 3.5 L/min air, pH 6.0, 7 days; 51 g/L sodium chloride, 99.01 ± 0.28% degradation |
This system contained dissolved air flotation (DAF), yeast bioreactor (yeast immobilized on policyurepan), upflow anaerobic sludge blanket reactor (UASB), and biological aerated filter [53] | Oilfield wastewater (145 mg oil/L) |
60 days, 99.6% oil degradation |
Native halophilic bacterial consortium immobilized on walnut shell [54] | Synthetic oilfield-produced water (191 mg/L oil) | 48 days, moving bed biofilm reactor, 97.8% oil degradation |
Methanogenic culture derived from a high-temperature oil reservoir production water [55] | Paraffinic n-alkanes (C22–C30) |
97% degradation and biogas accumulation, 736 days |
Consortium immobilized in cryogel of poly (vinyl alcohol): AC1 (80% anaerobic sludge plus 10% Desulfovibrio vulgaris plus 10% Clostridium acetobutilycum) for the straight-run gasoline fraction (Nafta) and AC3 (70% anaerobic sludge plus 10% D. vulgaris plus 10% C. acetobutilycum plus 5% Rhodococcus ruber plus 5% Rhodococcus erythropolis) for the straight-run diesel oil raction, non-hydrotreated vacuum gas oil, gas condensate, and crude oil [56] |
Sulfur-containing extracts from pre-oxidized crude oil, non-purified vacuum gas oil, straight-run gasoline fraction (Naphtha), gas condensate and straight-run diesel fraction (7–10 g/L COD) |
Biotransformation in methanogenic anaerobic reactor, 100% conversion of S-organic compounds to inorganic sulfide or biomass, biogas accumulation with 68–76% of CH4 for 20 days |
Consortium immobilized in cryogel of poly (vinyl alcohol): AC6 (80% anaerobic sludge plus 10% Rhodococcus opacus plus 10% Desulfovibrio desulfuricans) [57] |
Sulfur-containing extracts from pre-oxidized crude oil and oil fractions with hydrolysates of chicken manure and Chlorella vulgaris biomass (6.4–16 g/L COD) | Biotransformation in methanogenic anaerobic reactor, 100% conversion of S-organic compounds to inorganic sulfide or biomass, biogas accumulation with greater than 70% of CH4 for 6–42 days |
Consortium immobilized in cryogel of poly(vinyl alcohol): AC6 (80% anaerobic sludge plus 10% R. opacus plus 10% D. desulfuricans) and AC7 (90% adapted DEAMOX sludge plus 10% anaerobic sludge) [57] |
Sulfur-containing extracts from non-purified vacuum gas oil with hydrolysates of chicken manure and Chlorella vulgaris biomass (6.4 g/L COD) |
The two-stage biotransformation in methanogenic anaerobic reactor (MAR) and denitrifying ammonium oxidation (DEAMOX) reactor; 100% conversion of S-organic compounds to inorganic sulfide or biomass, biogas accumulation with 70% of CH4 for 20 days |
Combination of BCs with nanomaterials | ||
S. aestuarii 357 [58] | Naphthalene (0.128 mg/L) |
Two stages: (1) the formation of the naphthalene@FeNP-NDI-DA complex with FeNP-NDI-DA nanoparticals; (2) addition of S. aestuarii 357; 100% biodegradation |
Brevibacillus parabrev 1.13 × 108 cells/mL [59] |
Oily wastewater: Tetradecane 3% | Magnetic NPs of Fe3O4 (10 nm) 76% tetradecane was degraded by cells for 15 days |
Halamonas sp., Vibrio gazogenes or Marinobacter hydrocarbonoclasticus [60] | Crude oil (375 mg/L) | Polyvinylpyrrolidone (PVP)-coated iron oxide NPs (11.2 nm) 100% oil degradation for 24–48 h |
M. hydrocarbonoclasticus [61] | Crude oil (0.5% w/v) | Facile chemical modification of mesoporous silica NPs (mSNPs) (10 nm) 100% oil degradation for 45 days |
Bacillus cereus 1.55 × 105 cells/mL [16] |
PAHs: Anthracene, phenanthrene | Graphene oxide quantum dots (GOQDs) 52.7% degradation of PAHs for 3.5 days (1.7% degradation in control sample) |
Consortium in membrane bioreactor [62] |
Petroleum refinery wastewater (52.2 mg/L COD) |
Membrane bioreactor (MBR)-H2O2/UV Hybrid pretreatment before nanofiltration 80% of COD degradation for 1 h |
Pollutants [Reference] |
NCs/NCs; Size (nm) Physical or/and Chemical Treatment |
BC/Co-Substrate | Removal Efficiency (%) |
---|---|---|---|
Naphthalene, Phenanthrene, Anthracene, Fluoranthene, Pyrene (PAHs) in soil (200 mg/kg) [71] |
Ag3PO4@Fe3O4 UV-visible light photocatalyst (100–300 nm) |
Adapted consortium (sewage sludge) in microcapsules of Ca-alginate gel and carboxymethyl cellulose | 94% of PAHs mixture, ~100% of naphthalene, phenanthrene, anthracene, ~93% of fluoranthene, pyrene for 30 days |
Phenanthrene in water (PAH) [72] | Composite Mn3O4/MnO2-Ag3PO4 photocatalyst under visible light illumination |
Biofilms with Shewanella, Sedimentibacter, Comamonas, Acinetobacter and Pseudomonascells | 96.2% degradation for 20 min, 100% non-toxic intermediates for 10 h |
Phenanthrene in water [73] |
Cu/N-codoped TiO2 photocatalyst under UV or visible light illumination | PAH-degrading bacterial consortium with Pseudomonadaceae cells | UV (88.63% ± 0.71%) or visible light (62.87% ± 2.19%) from 10 mg/L for 6 h at room temperature; 9.31% ± 0.82% when only cells as BCs are used |
Pyrene (PAH) [74] | Cu/N-codoped TiO2 photocatalyst under visible or UV light illumination | PAH-degrading bacterial consortium | 63.89% ± 1.03% (Visual light biol. treatment) >61.27% ± 1.08% (UV biol. treatment) >59.58% ± 1.15% (UV) >57.41% ± 1.13% (Visual light) >6.65% ± 0.72% (biol. treatment) >1.70% ± 0.34% (control) |
Phenol, 4-chlorophenol (4-CP), and 4-fluorophenol (4-FP) [75] | N-doped TiO2 (30 nm) coated POHFs/combined UV and visible light | Microbial consortium: Scenedesmus obliquus (S. obliquus) biofilm with Rhodococcus and Pseudomonas cells |
The removals of DOC and COD of the phenolic compounds in mixture (1.06 mM phenol, 0.39 mM of 4-CP and 0.45 mM of 4-FP) for 11 h are ~98% and ~91%, respectively |
Toluene [70] | N-doped TiO2/PP | Microbial consortium |
99%, with the elimination capacity of 550 g/m3/h |
1,2,4 trichlorobenzene [76] | Sugarcane cellulose-TiO2 | Microbial consortium |
68.01%, which is 14.81% higher than that of biodegradation or photocatalysis alone, and the mineralization rate is 50.30%, which is 11.50% higher than that of photocatalysis alone |
Phenol (100 mg/L) [77] | CdS@SiO2@TRP nanocomposite photocatalyst under intermittent visible light irradiation | Adapted Pseudomonas putida cells |
Simultaneous removal 97.24% of phenol for 10 h |
Petroleum refinery wastewater [67] | Anatase nanocrystalline particles TiO2 (14 nm), catalyst concentration | Microbial consortium in Membrane Bioreactor, pH 10 | 100 mg/L of TiO2; 32% and 67% of TOC and TN for 90 min |
Benzene (100 mg/L), toluene(100 mg/L), and xylene (100 mg/L) [78] | Zinc sulfide (ZnS) nanoparticles (20–90 nm), UV-A light, 28 °C, pH 4 | Aspergillus niger | 100% for 1 h |
This entry is adapted from the peer-reviewed paper 10.3390/app13095815