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Weak interaction between flocculants and oil is a main bottleneck in the treatment of oil-containing wastewater. To solve this problem, a novel flocculant PAB with cationic micro-block structure and hydrophobic groups of benzene rings was synthesized by ultrasound initiated polymerization technique and applied to remove turbidity and oil from water. To avoid unnecessary addition of reagents in traditional template and micellar copolymerization, surface-active monomer benzyl(methacryloyloxyethyl)dimethylammonium chloride (BMDAC) with self-assembly ability in aqueous solution was employed to synthesize flocculants. The critical association concentration of BMDAC measured by conductivity and surface tension methods was 0.014 mol·L −1 . The results of reactivity ratio, statistical analysis of sequence-length distribution and 1 H NMR provided evidence for the synthesis of copolymer with cationic micro-block. In addition, the apparent viscosity measurement indicated that PAB had an obvious hydrophobic association property. Finally, flocculation tests demonstrated that flocculation performance was greatly improved by adding PAB and the removal rate of oil and turbidity both reached the maximum (87.5% and 92%) at dosage of 40 mg·L −1 and pH of 7.0. Flocculation mechanism investigation demonstrated that the cooperation of charge neutralization, adsorption bridging, and hydrophobic association effect played an important role. The formed flocs by PAB was large, compact, difficult to break, and easy to regrow because of the enhanced interaction between flocculants and oil. In summary, this study can provide important reference in the design of organic flocculants in oily wastewater treatment applications. [ABSTRACT FROM AUTHOR]

Modified natural polymer flocculants has been the focus of research in environmental engineering field. Natural large molecular compound, chitosan (CTS) with many functional amino and hydroxyl groups can be easily modified to enhance its original functions. This work presents an environmentally friendly chitosan-based cationic polyacrylamide flocculants (CTS-g-PAMA) with enhanced function of sterilization and flocculation. CTS-g-PAMA was synthesized through Ultraviolet (UV)-initiated copolymerization. Structure characterization of FTIR, 1 H NMR, XRD and UV spectrum confirmed the successful grafting of AM and MAPTAC. Scanning electron microscopy (SEM) analysis results showed that CTS-g-PAMA exhibited a porous structure with a prodigious surface area. CTS-g-PAMA was then applied to treat a series of simulated waste water containing kaolin or Escherichia coli . Flocculation tests indicated that CTS-g-PAMA not only showed excellent flocculation effect but also showed high sterilization capability. A series of ONP concentration measurement tests through UV spectra analysis and 3D EEM analysis of suspension before and after flocculation were conducted to study sterilization mechanism, and results revealed the sterilization effect of CTS-g-PAMA was essentially bactericidal, not just antibacterial. [ABSTRACT FROM AUTHOR]

Highlights: [•] A novel cationic flocculant P(AM–DAC–BA) was synthesized and characterized. [•] P(AM–DAC–BA) was synthesized through ultraviolet (UV) initiation. [•] P(AM–DAC–BA) prepared in quartz reactor was porous structure. [•] Comparison between quartz reactor and glass reactor was well studied. [•] P(AM–DAC–BA) was efficient in the dewatering of the textile sewage sludge. [ABSTRACT FROM AUTHOR]

• Amphiphilic CPAM was fabricated through ultrasonic initiated template polymerization. • Comparative characterizations confirmed the microblock structure and amphiphilicity. • Template copolymerization met bimolecular termination of free radical polymerization. • The effect of NaPAA followed template polymerization I (ZIP) mechanism. • Cationic microblocks produced stronger flocs to form more permeable filter cakes. Flocculation is an important pretreatment technique for sludge dewatering, the performance of employed flocculants is the key factor determine the flocculation efficiency. Herein, an amphiphilic cationic polyacrylamide (CPAM) with microblock structure was synthesized through template copolymerization initiated by ultrasonic. The chemical components and cationic microblock structure of copolymers were confirmed through comparative characterization by Fourier Transform Infrared (FTIR) and Nuclear Magnetic Resonance (1H NMR) spectrum. The copolymerization mechanism was investigated through kinetics study and association coefficient (K M) determination. The results indicated that the reaction followed free radical copolymerization and terminated mainly through bimolecular termination. The pre-adsorption between acryloyloxyethyltrimethylammonium chloride (DAC) and sodium polyacrylate (NaPAA) before reaction confirmed the template polymerization met the type I (ZIP) mechanism. Cationic microblocks and hydrophobic association together contributed to the optimal dewaterability (FCMC=67.2 %, SRF=3.84×1012 m·kg−1) using TP(AM-DAC-LA). Hydrophobic association enhanced bridging and sweeping effect to promote the floc size growth. Cationic microblocks produced compacter flocs with stronger mechanical strength through enhanced charge neutralization and patching effects, which acted as skeletons to make filter cakes less compressible and more permeable in mechanical dewatering. This work developed a highly effective flocculant for sludge dewatering, the synthesis and working mechanism of which were also given. [ABSTRACT FROM AUTHOR]

Natural polymeric flocculants as sludge conditioners have received great attention due to their non-toxic and biodegradable advantages. However, the application of amphiphilic natural flocculants as sludge conditioners is rarely reported. In this work, the novel chitosan-based flocculants (CS-g-PAO) with amphiphilic structure were synthesized by ultraviolet light initiated method for the enhancement of sludge dewatering performance. The solubility of CS-g-PAO was significantly improved in a wide pH range (2.0–10.0). Various characterization methods were used to investigate the structure, thermal stability and surface morphology of copolymers, suggesting the successful synthesis of CS-g-PAO. In dewatering experiments, CS-g-PAO showed superior dewatering performance, and filter cake moisture content could be decreased to 77.98% from 95.14%. Moreover, the results of extracellular polymeric substances (EPS) components indicated that hydrophobic effect of CS-g-PAO was beneficial to remove the protein in S-EPS and TB-EPS, which had the crucial influence on dewatering performance. Furthermore, the dewatering mechanism was discussed based on the effects of zeta potential, apparent viscosity, surface tension and flocs structure on dewaterability. Results revealed that CS-g-PAO had strong hydrophobic association effect and surface activity. In addition, enhanced charge neutralization and hydrophobic interaction played a synergetic role in improving the dewaterability of CS-g-PAO. Image 1 • A novel chitosan-based flocculant with amphiphilic structure was synthesized. • The water solubility of the amphiphilic flocculant was improved in a wide pH range. • The amphiphilic flocculant showed superior dewatering efficiency under low dosage. • All results confirmed the role of charge neutralization and hydrophobic attraction. [ABSTRACT FROM AUTHOR]

• The relationship between coagulation-flocculation and sterilization was emphasized. • Two flocculants played the different roles in drinking water treatment. • The synergistic effect of two coagulants for sterilization was confirmed by Contour Method. • Sterilization mechanism and kinetics of flocculants were revealed for the first time. • Sterilization was divided into two processes, rapidly adsorbing and slowly killing. In this study, the relationship between coagulation-flocculation and sterilization was studied using two conventional flocculants, polyaluminum chloride (PAC) and poly dimethyl diallyl ammonium chloride (PDMDAAC). Simulated wastewater containing kaolin and Escherichia coli was prepared. The bacterial removal rates of PAC and PDMDAAC under the same dosage are 46.3% and 19.5%, respectively. Which is far less than that of combined flocculants (94% bacterial removal rate). The synergistic effect of two flocculants was proved by contour method. β-Galactosidase activity, extracellular polysaccharides release, bacterial respiration activity and the activity of triphenyl tetrazolium chloride (TTC) dehydrogenase were investigated to clarify the sterilization kinetics and mechanisms. Two flocculants play the different roles in the treatment. PAC plays role of coagulation, charge neutralization, but PDMDAAC with quaternary ammonium groups is responsible for flocculation to form big flocs, which further enhances its contact with E. coli and contributes to sterilization. Sterilization by flocculants is divided into two processes, rapidly adsorbing and slowly killing, since the respiratory activity of E. coli in flocs gradually decreases with increasing contact time. The increase of flocculant dosage overcomes the hindrance of the secretion of extracellular polysaccharide polymers originating from E. coli to coagulation and sterilization. Sterilization of flocculant should be fully considered in drinking water treatment. [ABSTRACT FROM AUTHOR]

A novel chelating flocculant with branched architectures, polyacrylamide grafted maleoyl chitosan-mercaptoacetic acid (PAM-g-M(CS-MA)), was successfully fabricated using maleic anhydride as the "bridge" between chitosan and polyacrylamide. The functional groups and structural characteristic information of copolymers were obtained via characterization analysis. Flocculation performance was systematically investigated via purifying a series of simulated wastewater containing Cu or Cd. The properties of the flocs were studied to give in-depth evidences for the role of chelation groups and branched architectures in flocculation. Results indicated that PAM-g-M(CS-MA) showed excellent flocculation capacity for heavy metals in high concentrations and was superior to other chelating flocculants. The maximum flocculation efficiency of Cu (93.90%) and Cd (92.47%) was achieved by PAM-g-M(CS-MA) at pH 7, dosage of 100 mg L−1 and stirring speed of 90 rpm. The flocculation mechanisms of PAM-g-M(CS-MA) were deeply explored through the analyses of floc properties. The strong synergistic chelation of mercapto, carboxyl, amide and hydroxyl groups predominated for the capturing of heavy metals; and the branched architectures facilitated the formation of large and stable flocs via adsorption and bridging-furl effect. This study provided a solid foundation for the fabrication of flocculants for heavy metal wastewater treatment. [Display omitted] • A flocculant with branch architectures (PAM-g-M(CS-MA)) was synthesized. • PAM-g-M(CS-MA) showed low-dosage and efficient in heavy metals removal. • The maximum removal rates of Cu (93.90%) and Cd (92.47%) can be achieved by PAM-g-M(CS-MA). • Relationship between the branch architectures and flocculation performance was built. • Flocculation mechanism is composed by synergistic chelation, adsorption and bridging-furl effect. [ABSTRACT FROM AUTHOR]

The fine molecular structure of a flocculant fundamentally determines the internal flocculation mechanism and the final application property. In this work, three series of chitosan-based polymers (CTS-g-PAMD) with divergent charge densities and graft chain distribution were synthesized by graft copolymerization using acrylamide (AM) and acryloyloxyethyltrimethylammonium chloride (DAC). Meanwhile, flocculant with linear chain structure (CTS-CTA) was prepared by etherification using 3-chloro-2-hydroxypropyltrimethylammonium chloride (CTA). The characterization results confirmed that various monomers had been successfully introduced into chitosan. The reaction basically happened on —NH 2 at C 2 of chitosan, and the ring structure of chitosan was destroyed by free radical reaction. The obtained flocculants were used to flocculate bentonite and humic acid solution. Besides dose, the effects of chain structure, charge density and chain distribution on flocculation performance were systematically studied. Based on the fractal theory and flocculation kinetics, the effects of structural factors on floc characteristics were also investigated. The results showed that, flocculant with abundant graft chains exerts better flocculation performance and floc characteristic due to enhanced adsorption electrical neutralization and adsorption bridging effect. The effects of charge density and chain distribution on the flocculation performance were disparate in the range of insufficient and excessive doses. Furthermore, on the basis of the quadratic polynomial model, quantitative structure-effect relationships were established, which has guiding significance for the development and utilization of flocculants. Image 1 • Four chitosan-based flocculants with distinct molecular structures were prepared. • The cyclic structure of chitosan was destroyed by graft copolymerization. • Flocculants with "comb" branches exhibited better flocculation performance. • Chain distribution contributed differently under overdose and underdose. • The quantitative structure-activity relationships were established through model. [ABSTRACT FROM AUTHOR]

Chitosan-based flocculants are efficient and biodegradable, possessing the potential application in water treatment. A chitosan-based flocculant, CTS-g-PAM, was prepared via grafting copolymerization. Two main structures of CTS-g-PAM were detected by X-ray photoelectron spectroscopy (XPS), and they related to the different performances of CTS-g-PAM in the treatment of model azo dyeing wastewater in terms of removal efficiency, floc size and zeta potential. CTS-g-PAM with the optimal ratio of C N to –NH– owned the best performance. C N reinforced the interaction between CTS-g-PAM and azo dyes and charge neutralization while the flocs formed in the case were large and compacted. However, excessive C N accelerated itself hydrolysis and leaded to the decomposition of CTS-g-PAM, deteriorating the performance of the flocculant. Image 1 • Two different structures of CTS-g-PAM were discovered via XPS. • The ratio of two structures was different in various synthesis conditions. • The moderate C N in CTS-g-PAM contributed to its better performance in the treatment. • C N reinforced the interaction between CTS-g-PAM and azo dyes. • Excessive C N accelerated itself hydrolysis and decomposition of CTS-g-PAM. [ABSTRACT FROM AUTHOR]

• Dual-functional flocculant with pH resistant is synthesized and used to remove heavy metals. • Flocculation conditions for reaching high removal efficiencies are optimized. • Optimal operation modulus was identified using 8 Key performance indicators by 3E triangle model. • Multi-objective programming optimization model was also established to evaluate Operation strategies. • Flocculation for heavy metal removal is superior in terms of engineering performance. Carboxymethyl chitosan (CMCTS) with active hydroxyl and amino groups is easily modified for chelating and capturing heavy metal, thus showing great potential for application in heavy metal-contaminated wastewater treatment. In this work, a dual-functional MACA copolymer [CMCTS-graft-P(AM-TGA)] with pH resistant was successfully designed and prepared by grafting acrylamide and thioglycolic acid onto CMCTS through UV-initiated graft polymerization. The spectroscopy characterization of functional groups and apparent morphology confirm the successful preparation of MACA. Flocculation conditions for reaching high removal efficiencies and investigating chelation capacity are optimized. A multiobjective evaluation model and a triangular environmental impact, economic benefit, and energy consumption (3E) evaluation model were established and employed to assess the 3E performance of MACA in heavy metal-contaminated wastewater flocculation. Optimal operation modulus is identified using 8 Key performance indicators by 3E triangle model. This work enriches knowledge about flocculation and provides guidance for flocculation parameter control. [ABSTRACT FROM AUTHOR]