The ultralow interfacial tension between the oil and aqueous phases and the solubilization characteristics in microemulsion systems make them useful for surface cleaning and enhanced oil recovery applications. Microemulsions can form an adsorbed barrier on rock, reducing the acid-rock reaction rate. However, as acid retardation additives, the adsorption patterns of microemulsions are not clearly defined. In this study, microemulsions composed of various electrical surfactants, oil cores, and oil core additives were obtained, and their phase behaviors were investigated. Through adsorption and reaction experiments, cleaning microemulsions that enhance adsorption effects were identified, and their adsorption patterns and adaptability under flow conditions were evaluated. The results demonstrate that incorporating negatively charged polar compounds forms an enhanced adsorption microemulsion characterized by an average droplet size of less than 30 nm after mixing with the acid. The introduction of negatively charged polar compounds resulted in a 177 % increase in adsorption and an 81 % improvement in static retardation effect. Dynamic adsorption tests indicate that the pseudo-second-order model more accurately describes the kinetics of dynamic adsorption of microemulsions on rock surfaces. Under a fixed flow rate, the dynamic retardation rate increased with the concentration of the microemulsion. In practical acidification, the adsorption of microemulsions results mainly from combined electrostatic forces and fluid scouring, characterized by a continuous process of adsorption and desorption. Scanning electron microscope also confirmed that microemulsions can form an adsorptive film on the rock, reducing the acid-rock reaction rate. This study offers practical guidelines for the selection and application of retardation additives, aiming to enhance the ecological compatibility of chemical treatments in low-permeability limestone reservoirs.

Effective elimination of heavy metals from complex wastewater is of great significance for industrial wastewater treatment. Herein, bimetallic adsorbent Fe3O4-CeO2 was prepared, and H2O2 was added to enhance Sb(V) adsorption by Fe3O4-CeO2 in complex wastewater of Sb(V) and aniline aerofloat (AAF) for the first time. Fe3O4-CeO2 showed good adsorption performance and could be rapidly separated by external magnetic field. After five adsorption/desorption cycles, Fe3O4-CeO2 still maintained good stability. The maximum adsorption capacities of Fe3O4-CeO2 in single Sb(V), AAF + Sb(V), and H2O2+AAF + Sb(V) systems were 77.33, 70.14, and 80.59 mg/g, respectively. Coexisting AAF inhibited Sb(V) adsorption. Conversely, additional H2O2 promoted Sb(V) removal in AAF + Sb(V) binary system, and made the adsorption capacity of Fe3O4-CeO2 increase by 14.90%. H2O2 could not only accelerate the reaction rate, but also reduce the optimal amount of adsorbent from 2.0 g/L to 1.2 g/L. Meanwhile, coexisting anions had little effect on Sb(V) removal by Fe3O4-CeO2+H2O2 process. The adsorption behaviors of Sb(V) in three systems were better depicted by pseudo-second-order kinetics, implying that the chemisorption was dominant. The complexation of AAF with Sb(V) hindered the adsorption of Sb(V) by Fe3O4-CeO2. The complex Sb(V) was oxidized and decomposed into free state by hydroxyl radicals produced in Fe3O4-CeO2+H2O2 process. Then the free Sb(V) was adsorbed by Fe3O4-CeO2 mostly through outer-sphere complexation. This work provides a new tactic for the treatment of heavy metal-organics complex wastewater.

Graphene oxide (GO) has shown remarkable performance in the multiple-equilibrium-route adsorption (MER) process, which is characterized by further activation of GO through an in-situ reduction process based on single-equilibrium-route adsorption (SER), generating new adsorption sites and achieving an adsorption capacity increase. However, the effect of GO on MER adsorption in lateral size and thickness is still unclear. Here, GO sheets were sonicated for different lengths of time, and the adsorption of MER and SER was investigated at three temperatures to remove the typical cationic dye, acridine orange (AO). After sonication, we found that freshly prepared GO was greatly reduced in lateral size and thickness. In about 30 min, the thickness of GO decreased dramatically from several atomic layers to fewer atomic layers to a single atomic layer, which was completely stripped off; after that, the monolayer lateral size reduction dominated until it remained constant. Surface functional sites, such as hydroxyl groups, showed little change in the experiments. However, GO mainly reduces the C=O and C-O bonds in MER, except for the conjugated carbon backbone (C-C). The SER adsorption kinetics of all temperatures fitted the pseudo-first-order and pseudo-second-order models, yet room temperature preferred the latter. An overall adsorption enhancement appeared as sonication time, but the equilibrium capacity of SER GO generally increased with thickness and decreased with the single-layer lateral size, while MER GO conversed concerning the thickness. The escalated temperature facilitated the exfoliation of GO regarding the adsorption mechanism. Thus, the isotherm behaviors of the SER GO changed from the Freundlich model to Langmuir as size and temperature changed, while the MER GO were all of the Freundlich. A record capacity of ~4.3 g of AO per gram of GO was obtained from the MER adsorption with a sixty-minute ultrasonicated GO at 313.15 K. This work promises a cornerstone for MER adsorption with GO as an adsorbent.

Using cotton stalk as biomass raw material and phosphoric acid as a modifier, narrow pore distribution phosphorus-containing cotton stalk biochar (CSP) with a high surface area (1916 m2·g-1) and pore volume (1.3982 mL·g-1) was prepared through one-step carbonization, and the adsorption characteristics and mechanisms for tetracycline (TC) were investigated. The results showed that the TC adsorption capacity of CSP was up to 669 mg·g-1, which was 43.6 times that of unmodified cotton stalk carbon. FTIR, XPS, and isothermal adsorption studies showed that the high adsorption capacity of CSP for TC resulted from the joint action of complexation, hydrogen bonding, pore filling, and π-π dispersion forces, and the highly active phosphate ester group (P-O-C) endowed by phosphoric acid modification greatly enhanced the chemical interaction with TC molecules, which was the key factor for the significant increase in adsorption capacity. Isotherm and thermodynamic study further confirmed that chemical adsorption played a major role in the adsorption process, the adsorption process was spontaneous and endothermic, and the material had good regeneration performance. This study provides theoretical guidance for the preparation of modified biomass carbon with high adsorption performance to remove tetracycline antibiotic pollution.

Novel porous alginate-based nanocomposite hydrogels were prepared by incorporating polyaniline-polypyrrole modified graphene oxide (GO@PAN-PPy) as reinforcing fillers into the alginate matrix (GO@PAN-PPy/SA) for Cr(VI) and Cu(II) removal from water. Different in-situ co-polymerization functionalized GO with Py-to-An mass ratios of monomers (from nil to 1:1) and contents of GO@PAN-PPy (from nil to 2.0%(w/v)) were embedded into the alginate backbone to improve the sorption performance. Key factors, such as pH, coexisting metal ions, and swelling states were investigated in batch adsorption modes. The synergistic effect combined from polymer backbone and fillers could lower the impact of the pH-dependent adsorption reaction. With an adsorption ability superior to that of plain SA and GO/SA, the optimized GO@PAN-PPy-2(1)/SA exhibited good experimental maximum adsorption capacities for Cr(VI) (~133.7 mg/g) and Cu(II) (~87.2 mg/g) at pH 3.0, which were better than those of many other similar sorbents. The sorbents possessed excellent adaptability for 0.2 M salt for Cr(VI) removal but poor for Cu(II) removal. Pre-swelling treatment and co-adsorption could enhance the adsorption performance. The excellent reusability of hydrogel was demonstrated after five cycles in single/binary system. Overall, this work reveals that the resultant hydrogel holds potential as candidate sorbent to remove anionic-cationic heavy metal ions from water.

ABSTRACTPolycyclic aromatic hydrocarbons (PAHs) as polar organic pollutants, their potential harm to the environment has caused widespread concern. This study describes a simple method to prepare modified aerobic granular sludge (AGS) by hydroxypropyl-β-cyclodextrin (HP-β-CD). Using HP-β-CD modified AGS as the adsorbent, the removal of specific PAHs: Fluoranthene (Fla) reached 95% comparing to 80% of the unmodified AGS. The removal of Fla was related to initial concentration, temperature and ion concentration (Na+, Mg2+). The removal efficiency of Fla reached 96.27%, 94.26% and 93.69%, when initial concentration of Fla was 10 μmol/L, 15 μmol/L and 20 μmol/L. At temperatures of 15, 30 and 45 oC, the removal efficiency of Fla (15μmol L-1) gradually improved from 87.20% to 94.84% and 95.73%. The existence of Na+ and Mg2+ ions led to the deterioration of PAHs removal. With the increase of Na+ and Mg2+ concentrations, the removal efficiency of modified AGS on PAHs decreased by 3.9% and 6.5%, respectively. These findings indicate the potential application of cyclodextrins as the active sites of a complex modified polymer network for PAHs wastewater treatment.

A new two-step modification method has been proposed where 1.8% HCl and 3.1% HNO3 were applied to modify the interlayer of vermiculite (VMT). This product was given 90 °C of heat in 30% H2SO4 solution that was used for Pb (II) and Sb (III) adsorption. The EDTA presence on the individual adsorption was assessed. X-ray diffraction revealed that the VMT inter-stratified reflection through acid intercalation within the interlayer decreased the parallel gaps between the atoms, witnessing on the outer-sphere adsorption. The driving force was found electrostatic, which fits well with pseudo-second-order kinetics and Langmuir isotherm. The Pb (II) and Sb (III) uptake followed descending order adsorption with increasing concentration of chelating EDTA. Three consecutive desorption cycles revealed that the prepared adsorbent was suitable that may be regarded as a good candidate for complex wastewaters.

In this work, Zn-based coordination polymer [Zn2(1,3-bdc)bzim2]n was successfully synthesized by the sonochemical method using a 13 mm probe-type ultrasound operating at 20 kHz and amplitudes of 30, 40 and 50% corresponding to an acoustic power of 5.5, 8.6, and 10.3 W, respectively. Additionally, a sample was prepared by the slow-diffusion method for comparison. The samples were characterized by FTIR, PXRD, SEM, and BET techniques. The influence of the time and sonication amplitude on the yield of the reaction, crystallite size, and morphology were also studied. It was found that the sonochemical method provided the desired product in 83.9% within 20 min of sonication using the highest level of sonication amplitude. Moreover, this approach resulted in regular, controlled morphology, smaller particles, and higher surface area of the Zn-sample and derived oxide, than the slow diffusion method. The samples prepared by different methodologies were tested for the adsorption of BTEX (benzene, toluene, ethylbenzene, and xylenes) components in six different systems, and the uptakes were quantified by 13C NMR spectroscopy. Both samples showed excellent adsorption of benzene, 119.8 mmol/g, and 88.1 mmol/g, for the coordination polymers prepared via the sonochemical and slow-diffusion methods, respectively, corresponding to 63.9%, and 46.9%. These results are in agreement with the non-polar surface of these samples.