Bacterial cellulose as an oleaginous yeast cell carrier for soybean oil refinery effluent treatment and pyrolysis oil production.

Bacterial cellulose produced from soybean oil refinery effluent is a good immobilization carrier because of the large pores in its fiber network, its high water-holding capacity, and its good biocompatibility. In this study, it was applied to immobilization of oleaginous yeasts for treating soybean oil refinery effluent. The immobilization percentage reached 50%, and the removal of chemical oxygen demand and oil content reached 92.1% and 93.1%, respectively, during dynamic immobilization using a mass percentage of bacterial cellulose of 30% and an immobilization time of 24 h, which were significantly higher than those of free oleaginous yeasts or yeasts immobilized by bacterial cellulose from rich medium. The immobilized oleaginous yeasts facilitated the recovery of the yeasts and effectively treated three batches of soybean oil refinery effluent. The immobilized oleaginous yeasts recovered after soybean oil refinery effluent treatment were pyrolyzed to produce bio-oil, which contributed to more alkanes and a higher calorific value of bio-oil in the pyrolysis products as compared to those of free oleaginous yeasts. As bacterial cellulose used as an oleaginous yeast cell carrier is produced from soybean oil refinery effluent, no waste of immobilization materials is involved and an efficient waste-into-oil bioprocess is developed.

Submerged microfiltration membrane and activated carbon processes for recalcitrant compounds removal in oil refinery effluent as electrodialysis pre-treatment.

The combination of suspended activated carbon (AC) and submerged microfiltration (SMF) processes was applied to polish a biotreated effluent generated in a refinery industry. Preliminary results indicated that Norit 1240 W AC was more suitable than Carbomafra AC brand for total organic carbon (TOC) removal due to the highest Freundlich adsorption constant value (1.97 ± 0.42 and 0.96 ± 0.23 (mg/g)(L/mg)1/n, respectively), thus the first one was used in the combined system. Among all particle sizes of AC tested (0.041-1.01 mm), AC/SMF system was better performed, according to permeation flux, when applying granular AC instead of the powder one. On the other hand, the best response regarding TOC removal and absorbance at 254 nm (ABS254 nm) reduction were observed when applying powder AC (89% and 97%, respectively). Statistical analysis with two-sample T-test (p-value <0.05) endorsed the need of both air purge (20 L/h) and backwash strategies (8 min of permeation and 10 seconds of backwash) to diminish fouling occurrence in the SMF system. Finally, it was found that 2 g/L of Norit 1240 W PAC (0.041 mm particle size) condition fitted the effluent to further electrodialysis reversal (EDR) process (3.4 mg/L TOC) with consistent normalized permeate flux after 5 h of permeation (0.76 ± 0.1 J/J0).

Cancer and non-cancer health risk assessment of occupational exposure to 1,3-butadiene in a petrochemical plant in Iran.

1,3-Butadiene is classified as carcinogenic to humans by inhalation. This study aimed to assess cancer and non-cancer risk following occupational exposure to 1,3-butadiene. This cross-sectional study was conducted in a petrochemical plant producing acrylonitrile butadiene styrene copolymer in Iran. Occupational exposure to 1,3-butadiene was measured according to the National Institute for Occupational Safety and Health 1024 method. Cancer and non-cancer risk assessment were performed according to the United States Environmental Protection Agency method. The average occupational exposure to 1,3-butadiene during work shifts among all participants was 560.82 ± 811.36 µg m-3. The average lifetime cancer risk (LCR) in the present study was 2.71 × 10-3; 82.2% of all exposed workers were within the definite carcinogenic risk level. Also, the mean non-cancer risk (hazard quotient (HQ)) among all participants was 10.82 ± 14.76. The highest LCR and HQ were observed in the safety and fire-fighting station workers with values of 7.75 × 10-3 and 36.57, respectively. The findings revealed that values of carcinogenic and noncarcinogenic risk in the majority of participants were within the definitive and unacceptable risk levels. Therefore, corrective measures are necessary to protect these workers from non-cancer and cancer risks from 1,3-butadiene exposure.

Network between Cytokines, Cortisol and Occupational Stress in Gas and Oilfield Workers.

To test whether gas and oil field work is accompanied by stress and altered immune function, the perception of workplace stress, levels of salivary cortisol, plasma levels, and mononuclear cell production of cytokines were examined in 80 healthy workers recruited among a population of operators on gas and oilfields. Specific questionnaires for determining the perception of anxiety, occupational stress, and subjective symptoms were administered. Salivary cortisol and cytokines plasma levels were evaluated by Elisa and to investigate immune function, both spontaneous and PHA- or LPS-induced expression and production of cytokines were assessed by qRT-PCR. Workers showed medium stress levels at work, with growth and increased motivation for work, and based on salivary cortisol concentrations, were divided into two groups of ≤10 ng/mL (n = 31) or >10 ng/mL (n = 49). Statistically significant higher plasma levels of IL-6, while lower TNFα, were detected in workers with cortisol >10 ng/mL. Also, BMI, DL, JD and Job strain were significantly higher in workers with cortisol >10 ng/mL. Thus, even modest variations of cortisol might have a role in the modulation of immune response and worker's vulnerability to health imbalance.Thus, the evaluation of immune status, in addition to cortisol levels, could be useful to prevent illnesses; exacerbation of pre-existing conditions; morbidity; and consequent absences from work, with economic repercussions.

Use of plant materials for the bioremediation of soil from an industrial site.

Bioremediation is one of the existing techniques applied for treating oil-contaminated soil, which can be improved by the incorporation of low-cost nutritional materials. This study aimed to assess the addition of two low-cost plant residues, sugarcane bagasse (SCB) and leaf litter (LL) of the forest leguminous Mimosa caesalpiniifolia plant (sabiá), either separately or combined, to a contaminated soil from a petroleum refinery area, analyzed after 90 days of treatment. Individually, both amounts of SCB (20 and 40 g kg-1) favored the growth of total heterotrophic bacteria and total fungi, while LL at 20 g kg-1 better stimulated the hydrocarbon-degrading microorganism's activity in the soil. However, no TPH removal was observed under any of these conditions. Higher microbial growth was detected by the application of both plant residues in multicontaminated soil. The maximum TPH removal of 30% was achieved in amended soil with 20 g kg-1 SCB and 20 kg-1 LL. All the experimental conditions revealed changes in the microbial community structure, related to the handling of the soil, with abundance of Alphaproteobacteria. This study demonstrates the effectiveness of the plant residues SCB and LL as low-cost nutritional materials for biodegradation of hydrocarbon in real oil contaminated soil by indigenous populations.

The Application of Ferric Chloride-Lignin Sulfonate as Shale Inhibitor in Water-Based Drilling Fluid.

A series of ferric chloride-lignin sulfonate (FCLS) was prepared from ferric chloride and lignin sulfonate to be used as shale inhibitor. The swelling rate of clay with FCLS-2 (w/w = 0.3%) decreased to 41.9%. Compared with control, FCLS-2 displayed high inhibitive ability against the hydrating and swelling processes of clay. Thus, the swelling degree of samples with FCLS-2 was much lower than that of the control, as well as the mud ball was more stable in FCLS-2 solution. Essentially, these excellent performances in inhibitor were assigned to the hydrogen bonding, electrostatic interaction and anchoring between FCLS-2 and other components. In addition, FCLS-2 has good compatibility with other common drilling fluid additives, and it can reduce the viscosity of systems, regardless of the room temperature or high temperature.

Radiation induced in-situ cationic polymerization of polystyrene organogel for selective absorption of cholorophenols from petrochemical wastewater.

A new in-situ cationic polymerization was performed to synthesize a cross-linked (91%) polystyrene (PS) organogel through tetrachloroethylene radiolysis assisted by 60Co gamma rays. Hoernschemeyer diagram and swelling capacity test show a better selectivity of PS organogel to chlorinated molecules compared to ester, hydrocarbons and alcohols organic molecules by 80-184 folds. Response surface modeling (RSM) of CPs (2,4,6-trichlorophenol) sorption from artificial wastewater confirm superiority of PS organogel to absorb 1746 µmol CPs/g (∼345 mg CPs/g) at broad pH (4-10) and temperature (25-45 °C). Based on ANOVA statistic, simulated CPs absorption model onto PS organogel was successfully developed, with accuracy of prediction of R2≈ RAdj2 of 0.991-0.995 and lower coefficient of variation of 2.73% with Fmodel of 611.4 at p < .0001. Particularly, the usage of PS organogel for petroleum wastewater reclamation exhibited higher absorption affinities for all the organic contaminants especially for CPs (>99%) by non-covalent and/or dispersive interaction mechanisms with a well-term reusability and good stability up to 5 cycles.

The use of steel slags in the heterogeneous Fenton process for decreasing the chemical oxygen demand of oil refinery wastewater.

The Fenton process is a useful and inexpensive type of advanced oxidation process for industrial wastewater treatment. This study was performed with the aim of using the steel slag as a catalyst in the heterogeneous Fenton process in order to reduce the chemical oxygen demand (COD) of oil refinery wastewater. The effects of various parameters including the reaction time (0.5, 1.0, 2.0, 3.0 and 4.0 h), pH (2.0, 3.0, 4.0, 5.0, 6.0 and 7.0), the concentration of steel slag (12.5, 25.0 and 37.5 g/L), and H2O2 concentration (100, 250, 400 and 500 mg/L) on the Fenton process were investigated. Furthermore, the effect of microwave irradiation on the process efficiency was studied by considering the optimum conditions of the mentioned parameters. The results showed that using 25.0 g/L of steel slag and 250 mg/L H2O2, at pH = 3.0, could reduce COD by up to 64% after 2.0 h. Also, microwave irradiation decreased the time of the process from 120 min to 25 min in the optimum conditions, but it consumed a high amount of energy. It could be concluded that steel slags had a high potential in the treatment of oil refinery wastewater through the Fenton process.

Treatment of oilfield wastewater by combined process of micro-electrolysis, Fenton oxidation and coagulation.

In this study, a combined process was developed that included micro-electrolysis, Fenton oxidation and coagulation to treat oilfield fracturing wastewater. Micro-electrolysis and Fenton oxidation were applied to reduce chemical oxygen demand (COD) organic load and to enhance organic components gradability, respectively. Orthogonal experiment were employed to investigate the influence factors of micro-electrolysis and Fenton oxidation on COD removal efficiency. For micro-electrolysis, the optimum conditions were: pH, 3; iron-carbon dosage, 50 mg/L; mass ratio of iron-carbon, 2:3; reaction time, 60 min. For Fenton oxidation, a total reaction time of 90 min, a H2O2 dosage of 12 mg/L, with a H2O2/Fe2+ mole ratio of 30, pH of 3 were selected to achieve optimum oxidation. The optimum conditions in coagulation process: pH, cationic polyacrylamide dosage, mixing speed and time is 4.3, 2 mg/L, 150 rpm and 30 s, respectively. In the continuous treatment process under optimized conditions, the COD of oily wastewater fell 56.95%, 46.23%, 30.67%, respectively, from last stage and the total COD removal efficiency reached 83.94% (from 4,314 to 693 mg/L). In the overall treatment process under optimized conditions, the COD of oily wastewater was reduced from 4,314 to 637 mg/L, and the COD removal efficiency reached 85.23%. The contribution of each stage is 68.45% (micro-electrolysis), 24.07% (Fenton oxidation), 7.48% (coagulation), respectively. Micro-electrolysis is the uppermost influencing process on COD removal. Compared with the COD removal efficiency of three processes on raw wastewater under optimized conditions: the COD removal efficiency of single micro-electrolysis, single Fenton oxidation, single coagulation is 58.34%, 44.88% and 39.72%, respectively. Experiments proved the effect of combined process is marvelous and the overall water quality of the final effluent could meet the class III national wastewater discharge standard of petrochemical industry of China (GB8978-1996).

Response surface methodology approach for the optimisation of adsorption of hydrolysed polyacrylamide from polymer-flooding wastewater onto steel slag: a good option of waste mitigation.

Wastewater produced from polymer flooding in oil production features high viscosity and chemical oxygen demand because of the residue of high-concentration polymer hydrolysed polyacrylamide (HPAM). In this study, steel slag, a waste from steel manufacturing, was studied as a low-cost adsorbent for HPAM in wastewater. Optimisation of HPAM adsorption by steel slag was performed with a central composite design under response surface methodology (RSM). Results showed that the maximum removal efficiency of 89.31% was obtained at an adsorbent dosage of 105.2 g/L, contact time of 95.4 min and pH of 5.6. These data were strongly correlated with the experimental values of the RSM model. Single and interactive effect analysis showed that HPAM removal efficiency increased with increasing adsorbent dosage and contact time. Efficiency increased when pH was increased from 2.6 to 5.6 and subsequently decreased from 5.6 to 9.3. It was observed that removal efficiency significantly increased (from 0% to 86.1%) at the initial stage (from 0 min to 60 min) and increased gradually after 60 min with an adsorbent dosage of 105.2 g/L, pH of 5.6. The adsorption kinetics was well correlated with the pseudo-second-order equation. Removal of HPAM from the studied water samples indicated that steel slag can be utilised for the pre-treatment of polymer-flooding wastewater.

Application of PAC and flocculants for improving settling of solid particles in oilfield wastewater with high salinity and Ca2.

The suspended solids in wastewater from Rekabak oilfield, Kazakhstan, were characterized and treated with flocculants to enhance settling. The wastewater contained a high concentration of total dissolved solids and calcium ion. Scanning electron microscopy and energy dispersive X-ray analyses showed that suspended solids were mainly composed of corrosion products (iron oxides) and silicon dioxide particles. Also, much salt deposition from wastewater caused a large increase in the suspended solids value. The settling of solid particles in wastewater was investigated by turbidity decrease within 60 min. The particle settling was enhanced by adding polyaluminum chloride (PAC) as coagulant and hydrolyzed polyacryamide (HPAM) or cationic polyacrylamide (CPAM) as flocculant. At optimal dose, the particle settling ability with PAC and CPAM was better than that with PAC and HPAM. Particle size analysis showed that HPAM or CPAM with high molecular weight played an important role for enlarging the particle size. The experiments with simulated wastewater showed that particle settling by using HPAM deteriorated significantly compared to that by CPAM at high calcium ion. This study provides further understanding about the effect of high salinity and Ca2+ on solids formation, flocculant performance and particle settling. Meanwhile, the results are also helpful to develop novel flocculants used for high salinity wastewater.

Oil refinery hazardous effluents minimization by membrane filtration: An on-site pilot plant study.

Experiments for treating two different types of hazardous oil refinery effluents were performed in order to avoid/minimize their adverse impacts on the environment. First, refinery wastewater was subjected to ultrafiltration using a ceramic membrane, treatment, which did not provide an adequate reduction of the polar oil and grease content below the maximal contaminant level allowed. Therefore the option of reducing the polar oil and grease contamination at its main emission source point in the refinery - the spent caustic originating from the refinery kerosene caustic washing unit - using an alkaline-resistant nanofiltration polymeric membrane treatment was tested. It was found that at a constant operating pressure and temperature, 99.9% of the oil and grease and 97.7% of the COD content were rejected at this emission point. Moreover, no noticeable membrane fouling or permeate flux decrease were registered until a spent caustic volume concentration factor of 3. These results allow for a reuse of the purified permeate in the refinery operations, instead of a fresh caustic solution, which besides the improved safety and environmentally related benefits, can result in significant savings of 1.5 M€ per year at the current prices for the biggest Portuguese oil refinery. The capital investment needed for nanofiltration treatment of the spent caustic is estimated to be less than 10% of that associated with the conventional wet air oxidation treatment of the spent caustic that is greater than 9 M€. The payback period was estimated to be 1.1 years. The operating costs for the two treatment options are similar, but the reuse of the nanofiltration spent caustic concentrate for refinery pH control applications can further reduce the operating expenditures. Overall, the pilot plant results obtained and the process economics evaluation data indicate a safer, environmentally friendly and highly competitive solution offered by the proposed nanofiltration treatment, thus representing a promising alternative to the use of conventional spent caustic treatment units.

Self-Replenishable Anti-Waxing Organogel Materials.

Solid deposition, such as the formation of ice on outdoor facilities, the deposition of scale in water reservoirs, the sedimentation of fat, oil, and grease (FOG) in sewer systems, and the precipitation of wax in petroleum pipelines, cause a serious waste of resources and irreversible environmental pollution. Inspired by fish and pitcher plants, we present a self-replenishable organogel material which shows ultra-low adhesion to solidified paraffin wax and crude oil by absorption of low-molar-mass oil from its crude-oil environment. Adhesion of wax on the organogel surface was over 500 times lower than adhesion to conventional material surfaces and the wax was found to slide off under the force of gravity. This design concept of a gel with decreased adhesion to wax and oil can be extended to deal with other solid deposition problems.

Ion-specific oil repellency of polyelectrolyte multilayers in water: molecular insights into the hydrophilicity of charged surfaces.

Surface wetting on polyelectrolyte multilayers (PEMs), prepared by alternating deposition of polydiallyldimethylammonium chloride (PDDA) and poly(styrene sulfonate) (PSS), was investigated mainly in water-solid-oil systems. The surface-wetting behavior of as-prepared PEMs was well correlated to the molecular structures of the uncompensated ionic groups on the PEMs as revealed by sum frequency generation vibrational and X-ray photoelectron spectroscopies. The orientation change of the benzenesulfonate groups on the PSS-capped surfaces causes poor water wetting in oil or air and negligible oil wetting in water, while the orientation change of the quaternized pyrrolidine rings on the PDDA-capped surfaces hardly affects their wetting behavior. The underwater oil repellency of PSS-capped PEMs was successfully harnessed to manufacture highly efficient filters for oil-water separation at high flux.

Distribution characteristics and ecological risk analysis of microplastics in sediments and effluents related to offshore oil and gas activities in the Bohai Sea, China.

Oil and gas activities are sources of marine microplastics (MPs) but have received less attention globally. This study assessed the distribution characteristics and ecological risks of MPs in 31 sediment samples and effluent samples of 5 oil and gas platforms related to offshore oil and gas activities in the Bohai Sea. The results showed that the mean abundance of MPs in sediment, produced water, and domestic sewage was 205.7 ± 151.5 items/kg d.w., 18 ± 11 items/L, and 26 ± 39 items/L, respectively. The MPs in sediments and effluents were dominated by transparent, rayon, and fibers <1 mm. Oil and gas activities may influence the abundance of MPs in the sediments. The sediments in the area were at a low level of risk, but some samples exhibited indexes beyond low levels. The mass of MPs carried by the effluents from oil and gas platforms in the Bohai Sea was less than that of other sources.

Cellulose nanofiber-poly(ethylene terephthalate) nanocomposite membrane from waste materials for treatment of petroleum industry wastewater.

Petroleum industry wastewater contains high level of crude oil and other types of organic substances that can cause immense harm to the agriculture, aquatic as well as terrestrial organisms. Organic solvent resistance of membranes is very important to treat such wastewater that contains high level of organic pollutants. This work reports the designing of a superhydrophilic and organic solvent resistant nanocomposite membrane using waste bottles made of poly(ethylene terephthalate) (PET) and cellulosic papers. Using in-situ synthesized cellulose nanofibers we could successfully fabricate porous membranes which is not possible for bare PET matrix using water as nonsolvent. Thus, we could successfully replace methanol which was used as a suitable non-solvent in earlier reports by distilled water. We successfully used the membrane for separation of synthetic crude oil-water emulsion. The membrane showed permeability up to 98 Lm-2h-1 applying pressure of 1.5 bar. The membrane also achieved removal of more than 97 % of organic substances from a crude oil-water emulsion system. The optimum membrane also showed good thermal stability with initial degradation temperature ∼350 °C and tensile strength of 0.86 MPa. The antimicrobial property of the nanocomposite membranes could be achieved by coating its surface with carbon dots rooted graphene oxide.

Sustainable scale resistance on a bioinspired synergistic microspine coating with a collectible liquid barrier.

Scale deposition, especially in the petroleum industry, has always been a serious issue because of its potential safety hazards and huge economic cost. However, conventional scale-resistant strategies based on mechanical descaling and chemical detergents can't feed the urgent demand for energy saving and environmental protection. Herein, we report a bioinspired long-term oil collectible mask (BLOCK)-a microspine coating with the synergistic effect of anti-adhesion and oil collection, displaying sustainable scale resistance towards oilfield-produced water. Inspired by pitcher plants, the oil layer as a liquid barrier inhibits scale deposition by changing the underwater scaling micro-environment from liquid/solid/solid to a liquid/solid/liquid triphase system. Oil droplets are collected by cacti-inspired microspines to enhance oil layer stability. Compared with stainless steel, the BLOCK coating shows ca. 98% reduction even after 35 days in artificial produced water. This strategy could be utilized to design integrated functional materials for conquering complex environments such as oil recovery and transportation.

Antipsychotic drug waste: A potential corrosion inhibitor for mild steel in the oil and gas industry.

In this study, the corrosion inhibition efficiency of thioridazine hydrochloride (TH), an antipsychotic drug, on mild steel (commonly used pipeline material in the oil and gas industry) in 1 M hydrochloric acid (HCl) was evaluated using electrochemical techniques and weight loss method. Electrochemical impedance spectroscopy (EIS) results suggest that TH significantly enhances the polarization resistance (Rp) of mild steel. Similarly, potentiodynamic polarization results showed that the corrosion current density (icorr) of mild steel decreased significantly with addition of TH. To understand the long-term effect of TH, mild steel was tested for 7 days in 100 ppm TH containing electrolyte. EIS results showed that the Rp did not change significantly after 24 h exposure as compared to 2 h exposure; whereas the Rp increased by 28% after 7-day exposure. Weight loss measurements revealed that the inhibition efficiency of TH is remarkably high (98.8%) after 7-day exposure. The adsorption free energy calculation suggests that at the initial stage (1-day) of mild steel exposure, TH was physically adsorbed onto the surface. However, at a later stage (7- day) the binding of TH was chemical, and hence the corrosion protection increased with increase in the exposure period. As compared to the wide range of corrosion inhibitors reported in the literature, TH has shown to be highly effective for mild steel. Thus, it can be suggested that TH drug waste is a potential corrosion inhibitor for mild steel pipelines in the oil and gas industry.

Investigations on influences of MWCNT composite membranes in oil refineries waste water treatment with Taguchi route.

Most of the 'oil refineries' severally pollutes the water resources by depleting their untreated waste water like cooling water, storm water and unsanitary sewage water. These wastewaters are to be treated with high care to protect the human, pebbles, plants, fish and other water animals and from harmful effects. The present study focused to treat the oil refinery wastewater by means of Multi wall carbon nanotube (MWCNT) coated Polyvinylidene Fluoride (PVDF) membrane. The main objectives are: to increases the life of filter, reduce the percolation flux and reduce the formation of antifouling in the filter by using MWCNT composite membrane in it. Different process parameters of the proposed water treatment process, like diameter of MWCNT (15 nm, 20 nm, 25 nm and 30 nm), operating pressure (3 bar, 4 bar, 5 bar and 6 bar), pH value (3, 5, 7 and 9) and temperature (25 °C, 30 °C, 35 °C and 40 °C) temperature. Taguchi statistical technique is employed for designing experiments and for optimizing the process parameters of wastewater treatment process of an oil refinery. The proposed filter for wastewater treatment exhibited appreciable performance in removal rate of Percolation flux, percentage of chemical oxygen demand removal and percentage of total carbolic rejection as 27.2 kg/m2h, 78.51% and 95.33% respectively.