Preparation and Characterization of Magnetic Resin Made from Chitosan and Cerium

In this study, the water-based ferromagnetic fluid and magnetic resin made from chitosan and cerium complex （MRCCC） were successfully prepared by using the chemical co-precipitation technique and by the reversed-phase suspension cross-linking polymerization. MRCCC presented uniform and narrow panicle size distribution as determined by the Laser Panicles Sizer. The Inductively Coupled Plasma-Atomic Emission Spectrometry （ICP-AES）, Fourier transform infrared spectroscopy （FT-IR）, differential scanning calorimetry （DSC） and X-ray powder diffraction （XRD） study demonstrated that there were iron and cerium existing in MRCCC. The movement of MRCCC under magnetic field proved its magnetic property. The swelling kinetics in water or solutions with different pH indicated that MRCCC could be applied in solutions with pH greater than 1.0. The ferromagnetic fluid particles were stable in MRCCC soaked in solutions with pH 〉2.0. In view of these results, MRCCC can be used as material for separation, clarification, adsorption, sustained release and hydrolysis activity.

Preparation of a novel magnetic resin for effective removal of both natural organic matter and organic micropollutants

A novel, bifunctional, hypercrosslinked, magnetic resin W2 was prepared using divinylbenzene （DVB） and glycidyl methacrylate （GMA） as comonomers in three steps （i.e., suspension polymerization, amination and post-crosslinking reactions）. To evaluate the adsorption of natural organic matter （NOM） and organic micropollutants （OMPs） on the obtained resin W2, two magnetic resins W1 （the precursor of W2 before post-crosslinking） and W0 （the precursor of W1 before amination） were chosen for comparison. The results indicated that W2 would be a promising material for the removal of both NOM and OMPs from aquatic environments.

Combination of chlorine and magnetic ion exchange resin for drinking water treatment of algae

The effectiveness of a magnetic ion exchange resin （MIEX） for the treatment of Hongze Lake water in China was evaluated, The kinetics of natural organic matter （NOM） removal at various MIEX doses and contact time, multiple-loading experiments, impacts of MIEX prior to coagulation on coagulant demands and the effectiveness of combination of MIEX, pre-chlorination and coagulation were investigated. Kinetic experimental results show that more than 80% UV254 and 67% dissolved organic carbon （DOC） from raw water can be removed by the use of MIEX alone. 94% sulfate, 69% nitrate and 98% bromide removals are obtained after the first use of MIEX in multiple-loading experiments. It is suggested that MIEX can be loaded up to 1 250 bed volume （BV, volume ratio of tested water to resin） or more without saturation when regarding organics removal as a target. MIEX can remove organics to a greater extend than coagulation and lower the coagulant demand when combining with coagulation. Chlorination experimental results show that MIEX can remove 57% chlorine demand and 77% trihalomethane formation potential （THMFP） for raw water. Pre-chlorination followed by MIEX and coagulation can give additional organic and THMFP removals. The results suggest that MIEX provides a new method to solve thc problem algae reproduction.

Synthesis and Adsorption Studies on Magnetic Microbeads of Polythioether-arylamine Resins

By the suspended condensation reaction of poly(choloromethylthiirane)with o-tolidine and o- dianisidine respectively, two newmicrobeads chelating resins were synthesized by usingγ-Fe_2O_3 asmagnetic core. Their adsorption properties for Hg(Ⅱ), Cu(Ⅱ), Zn(Ⅱ), Pb(Ⅱ), Au(Ⅲ), Pd(Ⅱ), Pt (Ⅳ)and Ag(Ⅰ)were investigated. Themicrobeads posses excellent adsorbability for Hg(Ⅱ) and noble metalions, and predominantly adsorbed Pd(Ⅱ)or Hg(Ⅱ)in the coexistence ofCu(Ⅱ), Zn(Ⅱ)and Mg(Ⅱ).

17α-Ethinylestradiol removal from water by magnetic ion exchange resin

Magnetic ion exchange(MIEX) resins have received considerable attention in drinking water treatment due to their fast and efficient removal of dissolved organic carbon(DOC). Two types of mechanisms, i.e., ion exchange,reversible and irreversible adsorption, may occur during pollutants removal by MIEX. This work examined the removal mechanism of 17α-Ethinylestradiol(EE2) by MIEX. As one of typical estrogen micro-pollutants,EE2 existed as neutral molecule in natural water, and its charge density was close to zero [(0.00000219 ±0.00000015) meq·(μg EE2)^(-1)] based on the potentiometric titration method. However, the removal of EE2 by MIEX was much higher than that of other micro-pollutants previously reported. Multi-cycle adsorptionregeneration experiments and ion exchange stoichiometry analysis were conducted to elucidate the removal mechanism of EE2 by MIEX resin. The results suggested that the main removal mechanism of EE2 by MIEX was ion exchange instead of reversible micro-pore adsorption. The experimental analysis based on Donnan theory indicated that the internal micro-environment of resin beads was alkaline, in the alkaline environment EE2 would be ionized into negatively charged groups. As a result, ion exchange reaction occurred inside the pore of MIEX resin, and the removal process of EE2 by MIEX was dominated by the ion exchange reaction.

STUDY ON MAGNETIC CHELATING RESIN Ⅰ.PREPARATI0N OF PEI2 AND ITS ADSORPTION PROPERTIES TO METAL IONS

Magnetic polyethyleneimine chelating resin (PEI2) wasprepared. Its average diameter was 0. 44mm and it contained magnetic particles over 11% of the microcapsules after it had been treated with 8% hot HC1. The results showed that the reaction media had significant effect on physical forms, magnetic particles content and stability in acid of the microcapsules. PEF2 had very high adsorption capacity to Au3+ , Pd2+ and Hg2+ , and little one tmvards Mg2+, Pb2+ and Cu2+. It was discovered that PEI2 could reduce Au3+ into elemental gold.

STUDY ON MAGNETIC CHELATING RESIN Ⅱ.PREPARATION OF PSE2 AND ITS ADSORPTION PROPERTIES TO METAL IONS

Magnetic polythioether chelating resin (PSEZ) was pre-pared. Its average diameter was 0. 25mm and it contained magnetic parti-cles over 2,2% of the microcapsules after it had been treated with 2N hot HCl , and it ivould be destroyed in 5N hot HCl, The results showed that reaction medium had remarkable effect on physical forms of the microcap-sules. PSEZ had very high adsorption capacity to Au3+ and Hg2+, and little one towards Mg2+ , Pb2+. It was discovered that PSEZ could reduce Au3+ into elemental gold and Pti+to Pb2+.

3D printing of high-precision and ferromagnetic functional devices

The development of projection-based stereolithography additive manufacturing techniques and magnetic photosensitive resins has provided a powerful approach to fabricate miniaturized magnetic functional devices with complex three-dimensional spatial structures.However,the present magnetic photosensitive resins face great challenges in the trade-off between high ferromagnetism and excellent printing quality.To address these challenges,we develop a novel NdFeB-Fe_(3)O_(4) magnetic photosensitive resin comprising 20 wt.%solid loading of magnetic particles,which can be used to fabricate high-precision and ferromagnetic functional devices via micro-continuous liquid interface production process.This resin combining ferromagnetic NdFeB microparticles and strongly absorbing Fe_(3)O_(4) nanoparticles is able to provide ferromagnetic capabilities and excellent printing quality simultaneously compared to both existing soft and hard magnetic photosensitive resins.The established penetration depth model reveals the effect of particle size,solid loading,and absorbance on the curing characteristics of magnetic photosensitive resin.A high-precision forming and ferromagnetic capability of the NdFeB-Fe_(3)O_(4) magnetic photosensitive resin are comprehensively demonstrated.It is found that the photosensitive resin(NdFeB:Fe_(3)O_(4)=1:1)can print samples with sub-40μm fine features,reduced by 87%compared to existing hard magnetic photosensitive resin,and exhibits significantly enhanced coercivity and remanence in comparison with existing soft magnetic photosensitive resins,showing by an increase of 24 times and 6 times,respectively.The reported NdFeB-Fe_(3)O_(4) magnetic photosensitive resin is anticipated to provide a new functional material for the design and manufacture of next-generation micro-robotics,electromagnetic sensor,and magneto-thermal devices.

Dissolved organic matter removal using magnetic anion exchange resin treatment on biological effluent of textile dyeing wastewater

This study investigated the removal of dissolved organic matter（DOM） from real dyeing bio-treatment effluents（DBEs） with the use of a novel magnetic anion exchange resin（NDMP）.DOMs in two typical DBEs were fractionized using DAX-8/XAD-4 resin and ultrafiltration membranes. The hydrophilic fractions and the low molecular weight（MW）（〈3 kDa） DOM fractions constituted a major portion（〉50%） of DOMs for the two effluents. The hydrophilic and low MW fractions of both effluents were the greatest contributors of specific UV254absorbance（SUVA254）,and the SUVA254 of DOM fractions decreased with hydrophobicity and MW. Two DBEs exhibited acute and chronic biotoxicities. Both acute and chronic toxicities of DOM fractions increased linearly with the increase of SUVA254 value. Kinetics of dissolved organic carbon（DOC） removal via NDMP treatment was performed by comparing it with that of particle active carbon（PAC）. Results indicated that the removal of DOC from DBEs via NDMP was 60%,whereas DOC removals by PAC were lower than 15%. Acidic organics could be significantly removed with the use of NDMP. DOM with large MW in DBE could be removed significantly by using the same means. Removal efficiency of NDMP for DOM decreased with the decrease of MW. Compared with PAC,NDMP could significantly reduce the acute and chronic bio-toxicities of DBEs. NaCl/NaOH mixture regenerants,with selected concentrations of 10% NaCl（m/m）/1%NaOH（m/m）,could improve desorption efficiency.

Efficient adsorption and desorption of Cu^(2+) by a novel acid-resistant magnetic weak acid resin

A novel magnetic weak acid resin NDMC-1 was prepared in the presence of methyl acrylate （MA）, divinylbenzene （DVB） and titanate coupling agent （TCA） coated γ-Fe203 particles. To evaluate the adsorption of Cu^2＋ on the obtained resin NDMC- 1, another two magnetic resins NDMC-0 （the precursor of NDMC-1 without hydrolyzation） and NDMO-1 （the synthesized weak acid resin using oleic acid coated γ-Fe2O3） were chosen for comparison. The results showed that the carboxyl groups were formed after hydrolyzation, and NDMC-1 exhibited a greater adsorption capacity to Cu2~. The desorption experiment demonstrated that the desorption ratio at pH 2 （95.14%） was greatly higher than pH 3 （25.97%）. Moreover, the magnetic resin NDMC-1 was proved to be stable at pH 2, extending the application of magnetic materials which were always considered to be acid-nor, resistant.

Preparation of a permanent magnetic hypercrosslinked resin and assessment of its ability to remove organic micropollutants from drinking water

A rapid and effective method based on a novel permanent magnetic hypercrosslinked resin W150 was proposed for the removal of organic micropollutants in drinking water. W150 was prepared by suspension and post-crosslinking reaction and found to possess a high specific surface area of 1149.7 m^2· g^-1, a small particle size of 50 μm to 100 μm, and a saturation magnetization as high as 8 emu.g1. W150 was used to eliminate nitrofurazone （NFZ） and oxytetracycline （OTC） from drinking water compared with commercial adsorbents XAD-4 and F400D. The adsorption kinetics of NFZ and OTC onto the three adsorbents well fitted the pseudo-second-order equation （r 〉 0.972）, and the adsorption isotherms were all well described by the Freundlich equation （r 〉 0.851）. Results showed that the reduction in adsorbent size and the enlargement in sorbent pores both accelerated adsorption. Moreover, the effect of particle size on adsorption was more significant than that of pore width. Given that the smallest particle size and the highest specific surface area were possessed by W150, it had the fastest adsorption kinetics and largest adsorption capacity for NFZ （180 mg·g-1） and OTC （200mg·g- 1）. For the adsorbents with dominant micropores, the sorption of large-sized adsorbates decreased because of the inaccessible micropores. The solution pH and ionic strength also influenced adsorption.

Preparation of magnetic anion exchange resin and their adsorption kinetic behavior of reactive blue

Magnetic anion exchange resin （MD-1） was prepared from quaternization of magnetic copolymeric resin （glycidyl methacry- late-co-divinylbenzene）. For comparison, magnetic resin MD-0 without quaternization and non-magnetic resin （D-l） were also synthesized for the adsorption process. It was found that the adsorption was mainly contributed to the chemical interaction between quaternary ammonium groups and reactive blue RXHC. Due to the smaller size, MD- 1 had faster adsorption and desorption kinetics than D-1. Coupled with the advantage of easy separation, the magnetic anion exchange resin was considered to be superior to common anion exchange resin in removal of reactive dye.

Preparation and application of a novel magnetic anion exchange resin for selective nitrate removal

A novel magnetic anion exchange resin NDM-1 was prepared through suspension polymerization and then functionalized with ammonolysis and alkylating agents.Its application for selective removal of nitrate was performed in comparison with MIEX.The results demonstrated that NDM-1 achieved higher efficiency in nitrate removal than MIEX did,with or without the existence of competing anion SO_4^2- ascribed to its longer alkyl chains on exchange sites.Combined with the advantage of easy separation due toγ-Fe_2O_3 implanted,the magnetic anion exchange resin NDM-1 was considered to be superior to MIEX for nitrate removal in practical application.

Selection of magnetic anion exchange resins for the removal of dissolved organic and inorganic matters

Four magnetic anion exchange resins （MAERs） were used as adsorbents to purify drinking water. The effect of water quality （pH, temperature, ionic strength, etc.） on the performance of MAER for the removal of dissolved organic matter （DOM） was also investigated. Among the four studied MAERs, the strong base resin named NDMP- 1 with high water content and enhanced exchange capacity exhibited the highest removal rate of dissolved organic carbon （DOC） （48.9% removal rate） and UV-absorbing substances （82.4% removal rate） with a resin dose of 10 mL/L after 30 rain of contact time. The MAERs could also effectively remove inorganic matter such as sulfate, nitrate and fluoride. Because of the higher specific UV absorbance （SUVA） value, the DOM in the raw water was found to be removed more effectively than that in the clarified water by NDMP resin. The temperature showed a weak influence on the removal of DOC from 6 to 26℃, while a relatively strong one at 36℃. The removal of DOM by NDMP was also affected to some extent by the pH value. Moreover, increasing the sulfate concentration in the raw water could decrease the removal rates of DOC and UV-absorbing substances.

Comparison of different combined treatment processes to address the source water with high concentration of natural organic matter during snowmelt period

The source water in one forest region of the Northeast China had very high natural organic matter（NOM） concentration and heavy color during snowmelt period. The efficiency of five combined treatment processes was compared to address the high concentration of NOM and the mechanisms were also analyzed. Conventional treatment can hardly remove dissolved organic carbon（DOC） in the source water. KMn O4pre-oxidization could improve the DOC removal to 22.0%. Post activated carbon adsorption improved the DOC removal of conventional treatment to 28.8%. The non-sufficient NOM removal could be attributed to the dominance of large molecular weight organic matters in raw water, which cannot be adsorbed by the micropore upon activated carbon. O3＋ activated carbon treatment are another available technology for eliminating the color and UV254 in water. However, its performance of DOC removal was only 36.4%, which could not satisfy the requirement for organic matter. The limited ozone dosage is not sufficient to mineralize the high concentration of NOM. Magnetic ion-exchange resin combined with conventional treatment could remove 96.2%of color, 96.0% of UV254 and 87.1% of DOC, enabling effluents to meet the drinking water quality standard. The high removal efficiency could be explained by the negative charge on the surface of NOM which benefits the static adsorption of NOM on the anion exchange resin. The results indicated that magnetic ion-exchange resin combined with conventional treatment is the best available technology to remove high concentration of NOM.