Starch microsphere silicon-boron crosslinker for low concentration hydroxypropyl guar gum based fracturing fluid.

Hydroxypropyl guar gum (HPG) is a critical thickener to increase viscosity and lubrication to improve the water-based hydraulic fracturing efficiency. However, current crosslinkers require a large amount of HPG (>0.3 wt%) to form gel with sufficient viscosity, and high concentrations of HPG may cause adverse effects to the production and the environment. In this study, a novel starch microsphere silica­boron crosslinker (SMSB) was developed using starch microspheres as a carrier and γ-aminopropyl triethoxy silane (KH550) as a modifier with an in-house method. Both the rheology and surface reactions of the SMSB-HPG crosslinking system were studied using multiple laboratory experiments and molecular dynamics simulation. The results showed that SMSB crosslinker caused multi-site cross-linking with low concentration (only 0.2 wt%) of HPG molecules, reducing the twisting of single molecular chain in the crosslinking system, enhancing the cross-linking strength between molecular chains, and making HPG molecular chains stretcher in the aqueous solution. The apparent viscosity and viscoelasticity of the HPG system were substantially higher than the organoboron crosslinker, and the temperature resistance of the SMSB-HPG crosslinking system was up to 140 °C. This study provides an alternative green crosslinker for more sustainable industrial applications and provides theoretical basis for the modification of biomaterials.

A Real-Time Monitoring Method for Droplet Transfer Frequency in Wire-Filled GTAW Based on Arc Sensing.

Droplet transfer frequency is a decisive factor in welding quality and efficiency in gas tungsten arc welding (GTAW). However, there still needs to be a monitoring method for droplet transfer frequency with high precision and good real-time performance. Therefore, a real-time monitoring method for droplet transfer frequency in wire-filled GTAW using arc sensing is proposed in this paper. An arc signal acquisition system is developed, and the wavelet filtering method filters out noise from the arc signal. An arc signal segmentation method-based on the OTSU algorithm and a feature extraction method for droplet transition based on density-based spatial clustering of applications with noise (DBSCAN)-is proposed to extract the feature signal of the droplet transition. A new conception of droplet transition uniformity is proposed, and it can be used to monitor the weld bead width uniformity. Numerous experiments for monitoring droplet transfer frequency in real time are conducted with typical welding parameters. This method enables the real-time observation of droplet transfer frequency, and the result shows that the average monitoring error is less than 0.05 Hz.

Efficient removal of Cr from aqueous solution by catechol/m-phenylenediamine nanospheres combined with Fe(II).

The discharge of chromium-containing wastewater in industrial production causes resource loss and damage to the ecological environment. Currently, various phenolamine materials have been used to remove chromium, but their harsh adsorption conditions bring many difficulties. For example, ideal chromium removal is only achieved at low pH. In this study, we synthesized catechol/m-phenylenediamine nanospheres (CMN) and combined CMN with Fe(II) for Cr removal from aqueous solutions, and Fe(II) comes from FeSO4·7H2O. CMN was characterized and analyzed by field-emission scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), transmission electron microscopy (TEM), Fourier transformed infrared (FTIR), X-ray diffraction (XRD), X-ray photoelectron (XPS). The adsorption performance was studied through a series of adsorption experiments. When C0 = 900 mg/L and pH = 6, the maximum adsorption capacity obtained in the experiment was 977.1 mg/g. It maintains excellent adsorption properties in acidic, neutral and alkaline environments. The results of the adsorption mechanism showed that the ultra-high adsorption capacity of CMN and Fe(II) for Cr was the result of the synergistic effect of adsorption and reduction, including electrostatic attraction, reduction and coprecipitation. CMN is expected to be an ideal adsorbent for Cr removal in aqueous solution due to its low cost, high biocompatibility and high efficiency in Cr removal.

Coupling iron-carbon micro-electrolysis with persulfate advanced oxidation for hydraulic fracturing return fluid treatment.

Improving the sustainability of the hydraulic fracturing water cycle of unconventional oil and gas development needs an advanced water treatment that can efferently treat flowback and produced water (FPW). In this study, we developed a robust two-stage process that combines flocculation, and iron-carbon micro-electrolysis plus sodium persulfate (ICEPS) advanced oxidation to treat field-based FPW from the Sulige tight gas field, China. Influencing factors and optimal conditions of the flocculation-ICEPS process were investigated. The flocculation-ICEPS system at optimal conditions sufficiently removed the total organic contents (95.71%), suspended solids (92.4%), and chroma (97.5%), but the reaction stoichiometric efficiency (RSE) value was generally less than 5%. The particles and chroma were effectively removed by flocculation, and the organic contents was mainly removed by the ICEPS system. Fourier-transform infrared spectroscopy (FTIR) analysis was performed to track the changes in FPW chemical compositions through the oxidation of the ICEPS process. Multiple analyses demonstrated that PS was involved in the activation of Fe oxides and hydroxides accreted on the surface of the ICE system for FPW treatment, which led to increasing organics removal rate of the ICEPS system compared to the conventional ICE system. Our study suggests that the flocculation-ICEPS system is a promising FPW treatment process, which provides technical and mechanistic foundations for further field application.

Treatment and recycling of acidic fracturing flowback fluid.

Acidic fracturing flowback fluid (AFFF) has the characteristics of low pH value, high chemical oxygen demand (COD), high corrosiveness and complex components. Surface discharge without treatment may contaminate the environment. However, wastewater treatment after centralized transportation has potential safety risks and requires high costs. In this study, we confirmed that calcium and magnesium could affect cross-linking property of fracturing fluid prepared by flowback fluid, and conducted a three-step process, two-stage filtration, chemical precipitation, and flocculation precipitation, on AFFF. After treatment, we made new hydraulic fracturing fluid using the treated acidic flowback fluid as base fluid and compared the quality of the new hydraulic fracturing fluid to the ones used freshwater as base fluid. The results showed when concentration of sodium carbonate, polyaluminium chloride (PAC), polyacrylamide (PAM) were 145, 1000, and 20 mg/L respectively, the treatment result was optimal. After treatment, the oil content of AFFF decreased from 7400 to 26.53 mg/L and suspended solids (SS) from 650 to 18.24 mg/L, and the removal rate of high-valence metal ions was more than 99%. The rheological properties and viscoelasticity of new fracturing fluid prepared by the treated AFFF were similar to the ones prepared by freshwater, which met the requirements of high temperature and shear resistance for ultra-deep wells.

Lead (Pb) sorption to hydrophobic and hydrophilic zeolites in the presence and absence of MTBE.

The co-contamination of the environment by metals and organic pollutants is a significant concern, and one such example is lead (Pb) and methyl tert-butyl ether (MTBE) due to their historic use as fuel additives. Clinoptilolite is an abundant and efficient zeolite for metal removal, but the potential interference of co-existing organic pollutants on metal removal, such as MTBE, have rarely been discussed. In this study, a combination of batch sorption tests and synchrotron-based X-ray absorption spectroscopic analyses were employed to investigate Pb sorption mechanism(s) onto clinoptilolite in the presence and absence of MTBE. A comparison was made to synthetic ZSM-5 zeolite to gain insights into differences in Pb binding mechanisms between hydrophilic (clinoptilolite) and hydrophobic (ZSM-5) zeolites. Site occupancy and surface precipitation contributed equally to Pb removal by clinoptilolite, while surface precipitation was the main Pb removal mechanism for ZSM-5 followed by site occupancy. Despite the negligible effect of 100 mg/L MTBE on observed Pb removal from solution by both zeolites, a surface-embedded Pb removal mechanism, through the Mg site on clinoptilolite surface, arises when MTBE is present. This study provides an understanding of atomic-level Pb uptake mechanisms on zeolites, with and without co-contaminating MTBE, which aids in their application in water treatment at co-contaminated sites.

Red-emission carbon dots-quercetin systems as ratiometric fluorescent nanoprobes towards Zn2+ and adenosine triphosphate.

Carbon dots (CDs) emitting red fluorescence (610 nm) were synthesized by solvent thermal treatment of p-phenylenediamine in toluene. Upon 440 nm excitation, quercetin (QCT) alone endowed slight effects on the red fluorescence of CDs. Once Zn2+ was further introduced, the QCT-Zn2+ complex was quickly formed. This complex absorbs excitation light and emits bright green fluorescence at 480 nm. The red fluorescence of CDs was greatly quenched owing to the inner-filter effect. The ratio of fluorescence intensity at 480 nm and 610 nm (I480/I610) gradually increases with increasing concentration (c) of Zn2+. Al3+ exhibits the same phenomen like Zn2+. Fluoride ions form a more stable complex with Al3+ than QCT-Al3+ complex but have a negligible effect on the QCT-Zn2+ complex. The possible interference of Al3+ on Zn2+ can thus be avoided by adding certain amount of F-. The CD-QCT-F- system was constructed as a ratio-metric fluorescent nanoprobe toward Zn2+ with determination range of 0.14-30 µM and limit of detection (LOD) of 0.14 µM. Due to the stronger affinity of adenosine triphosphate (ATP) to Zn2+ than QCT, the I480/I610 value of CD-QCT-F--Zn2+ system gradually decreases with increasing cATP. The ratiometric fluorescent nanoprobe toward ATP was established with detection ranges of 0.55-10 and 10-35 µM and a LOD of 0.55 µM. The above two probes enable the quantitative determination of Zn2+ and ATP in tap and lake water samples with satisfactory recoveries. Graphical abstract Schematic representation of the ratiometric fluorescent nanoprobes based on the carbon dots (CDs)-quercetin (QCT) system towards Zn2+ and adenosine triphosphate (ATP) with high selectivity and sensitivity.

One-pot synthesis of N-doped carbon dots by pyrolyzing the gel composed of ethanolamine and 1-carboxyethyl-3-methylimidazolium chloride and their selective fluorescence sensing for Cr(vi) ions.

N-Doped carbon dots (CDs) were directly synthesized with a high yield of 21.85% by one-pot pyrolysis of a gel composed of ethanolamine and 1-carboxyethyl-3-methylimidazolium chloride at 220 °C for 2 h. The as-synthesized CDs with a mean particle size of 7.8 nm were uniform, amorphous, and abundant in nitrogen content (23.15 wt%) and surface groups such as amide and hydroxyl. Thus, the CDs exhibited good water-solubility, bright blue excitation- and pH-dependent fluorescence with a quantum yield of 17.93%, and high ionic strength tolerance. In addition, a CD-based fluorescent sensor towards Cr(vi) ions with favorable sensitivity and selectivity was constructed based on the inner filter effect. Two good linear relationships between the concentration of Cr(vi) ions and the PL quenching efficiency were obtained in the ranges from 0.2 to 2 (R2 = 0.9965) and 2-40 µM (R2 = 0.9918), and the limits of detection (LOD = 3σ/S) were calculated as 0.018 and 0.25 µM, respectively. Importantly, this sensor was solid and capable of rapidly detecting Cr(vi) ions in tap water with detection ranges of 0.2-2 (R2 = 0.9817) and 2-60 µM (R2 = 0.9902), LODs of 0.048 and 0.40 µM, and recoveries of 102.1-106%.

Effects of ion pairing on the capillary electrophoretic separation and ultraviolet-absorption detection of quaternary ammonium cations using meso-octamethylcalix[4]pyrrole as the background electrolyte additive.

Five quaternary ammonium cations, including tetramethylammonium, tetraethylammonium, hexadecyltrimethylammonium, benzyltrimethylammonium, and 1-butyl-3-methylimidazolium, have been separated by capillary electrophoresis. A direct ultraviolet method has been achieved when tetrabutylammonium fluoride was the background electrolyte and meso-octamethylcalix[4]pyrrole was the background electrolyte additive. The ultraviolet spectra of meso-octamethylcalix[4]pyrrole and cation mixtures showed that redshifts can be attributed to the size of cations, and the maximum absorption wavelength shifted from 218 to 230 nm when tetrabutylammonium cation was substituted with tetramethylammonium cation or tetraethylammonium cation. Conductivity measurements were performed to evaluate the ion-pairing effect of tetrabutylammonium fluoride in a mixture of acetonitrile/ethanol (80:20, v/v), and the ion-pairing formation constant, Kip, was calculated (Kip = 14.8 ± 0.3 L/mol) using the Fuoss extended model. Ion pairing also occurs between cations of the analytes and counterion, a fluoride complex of meso-octamethylcalix[4]pyrrole. The tetramethylammonium cations associate more strongly with this counterion than the tetraethylammonium cation that contributes to the change of selectivity in capillary electrophoresis separation. The effective mobilities of the cations with trimethyl groups, such as tetramethylammonium cation, benzyltrimethylammonium cation, and hexadecyltrimethylammonium cation, decreased faster than others with the increase of meso-octamethylcalix[4]pyrrole concentration, highlighting the fact that the ion-pairing effect played an important role in this method.

Cation effects in the separation of calix[4]pyrroles by nonaqueous capillary electrophoresis with tetraalkylammonium chloride salts as background electrolytes.

The migration behavior of three calix[4]pyrroles (C4Ps) in acetonitrile (ACN) and in the mixtures of ACN/ethanol (EtOH) (95:5; v/v)with tetraalkylammonium chloride as background electrolyte (BGE) was studied. Electroosmotic flow (EOF) mobilities and absolute mobilities in ACN and mixture of ACN/EtOH (95:5; v/v) were investigated. A decrease of EOF mobilities in EtOH/ACN was observed compared with that of in pure ACN. Variation of the C4Ps effective mobilities as a function of the square root of concentration of tetraakylammonium chloride salts such as tetramethylammonium chloride (Me4NCl), tetraethylammonium chloride (Et4NCl) and tetrabutylammonium chloride (Bu4NCl) in both solvents was plotted, and straight lines were exhibited when Bu(4)NCl was used as BGE. Absolute mobilities of C4Ps were obtained by extrapolation from the mentioned plots. It was found that the absolute mobilities of C4Ps is independent of the nature of BGE and the values are: meso-octamethylcalix[4]pyrrole (OMCP)>meso-tetracyclopentylcalix[4]pyrrole (TPCP)>meso-tetracyclohexylcalix[4]pyrrole (THCP). The ion-pairing constants follow the order under given solvent: Me4N+>Et4N+>Bu4N+, and ion-pairing constant of C4P follows the order: THCP>TPCP>OMCP. As though, ion-pairing association is intensified by steric hindrance.

Hydrogen-bond effect and ion-pair association in the separation of neutral calix[4]pyrroles by nonaqueous capillary electrophoresis.

A study on the migration behavior of four neutral macrocyclic compounds calix[4]pyrroles (C4Ps) by nonaqueous capillary electrophoresis (NACE) with tetrabutylammonium halide salts as background electrolyte (BGE) is described. Systematic studies were carried out with different BGE in acetonitrile (ACN) to elucidate the involved phenomena. The effect of BGE concentration on analytes effective mobilities mu eff,i was studied. Rough values of analytes absolute mobilities mu infinity,i were obtained by extrapolation of effective mobilities to zero ionic strength of BGE. Stokes radius of C4Ps in the form of C4PF(-) and C4PCl(-) was calculated. The complex constants of C4Ps with F(-) anion and Cl(-) anion and ion-pair association constants of each C4PF(-) and C4PCl(-) with tetrabutylammonium cations was evaluated and confronted. Hydrogen bonding effect is prerequisite in the separation; meanwhile ion-pair association which is intensified by steric hindrance effect plays an important role.

Separation and determination of flavonoids in Lamiophlomis rotata by capillary electrophoresis using borate as electrolyte.

A capillary electrophoresis method was developed for the simultaneous determination of five flavonoids such as luteolin-7-O-glucoside, isorhamnetin, apigenin, luteolin and quercetin in Lamiophlomis rotata (Benth.) Kudo. Optimal conditions were obtained at pH 9.0 with 30 mM borate as buffer containing 8% (v/v) acetonitrile, 20 kV as driving voltage and 210 nm as detection wavelength. The association constant K and the change in Gibbs free energy (DeltaG) of the interaction of flavonoids with borate anion ion (a typical ion-dipole or ion-induced dipole interaction) were calculated for the quantitative evaluation and characterization of the interaction. The described method was successfully applied for the rapid and efficient quality control by quantifying flavonoids in L. rotata. Repeatability tests showed that the R.S.D.s of both intra- and inter-day migration times and peak areas were less than 5%. The LOD of the five flavonoids was less than 3.75 mg/l. Recovery results ranged from 94.2% to 105.1%.