Highly efficient recovery of phosphate and fluoride from phosphogypsum leachate: Selective precipitation and adsorption.

Phosphogypsum, a typical by-product in the phosphorus chemical industry, could generate a large amount of leachate containing phosphate and fluoride in the process of rainfall and long-term stacking, which not only causes serious environmental pollution, but also leads to a waste of resources. In this study, a united treatment of calcium hydroxide precipitation and lanthanum zeolite (La-ZFA) adsorption was proposed to achieve the recovery of phosphate and fluoride from phosphogypsum leachate. In phosphogypsum, most phosphorus could be leached except P in the residual occurrence form, while for fluoride, only water-soluble F could be effectively leached. The optimum leaching amounts of phosphate and fluoride were 22.59 and 4.64 mg/g, respectively, at liquid-solid ratio of 400:1, leaching time of 120 min, pH of 6.0, particle size of >200 mesh (<0.075 mm), and leaching temperature of 25°C. Using Ca(OH)2 as the precipitant, the phosphate could be precipitated selectively from phosphogypsum leachate by controlling pH and time, and the concentrations of it decreased significantly to 0.29 mg/L at pH 10.0, with a removal efficiency of 99.48%. XRD, SEM and Visual MINTEQ software analysis proved that the main component of the precipitate was hydroxyapatite (Ca5(PO4)3(OH)). After P precipitation, a series of sorbents for fluoride were investigated, and La-ZFA sorbent was chosen and utilized to recover the fluoride from the leachate through a cyclic fixed-bed column. The efficiency of La-ZFA was basically not affected by the high concentration sulfate, and it can selectively adsorb fluoride from phosphogypsum leachate, leading to a final fluoride concentration of 0.29 mg/L in the effluent. The characterization demonstrated that fluoride might be adsorbed onto the La-ZFA via ligand exchange with hydroxy groups. The proposed method in this study is expected to sequentially recover phosphate and fluorine from the leachate of phosphogypsum, and it has great guiding significance for resource utilization and management of phosphogypsum.

PPh3/I2 Promoted Synthesis of Unsymmetrical Disulfides from Sodium Sulfites and 2-Mercaptobenzo Heterocyclics.

A simple and efficient method for the synthesis of unsymmetrical disulfides is reported. Using sodium sulfites and 2-mercaptobenzo heterocyclic compounds as starting materials, the unsymmetrical sulfur-sulfur bonds could be quickly constructed in the PPh3/I2 reaction system under transition-metal-free conditions. This protocol has the advantages of mild reaction conditions, easily available starting materials, and wide substrate scope, showing potential synthetic value for the synthesis of a diversity of biologically or pharmaceutically active compounds.

Selective removal of phosphate from aqueous solution by MIL-101(Fe)/bagasse composite prepared through bagasse size control.

MIL-101(Fe)/sugarcane bagasse (SCB) with high adsorption capacity and selectivity toward phosphate was prepared through in-situ synthesis method. Effects of bagasse size on the morphology and performances of the composites were investigated, and adsorption behavior and mechanism of phosphate on the composite prepared at the optimum bagasse size were studied. Results showed that composite prepared with bagasse size of 200-300 mesh (MIL-101(Fe)/SCB3) showed much higher adsorption capacity than SCB, blank MIL-101(Fe) and the composites prepared with the other bagasse size, which was due to the more positively charged surface and the more exposed adsorption active sites including FeOHx and exchangeable Cl-. Co-ions experimental results illustrated that the as prepared MIL-101(Fe)/SCB3 showed high adsorption affinity toward phosphate, and the common cationic and anionic ions exhibited negligible effects on phosphate adsorption capacity and rate. The optimum pH range for phosphate adsorption on MIL-101(Fe)/SCB3 was from 3.0 to 10.0, and in this range Fe release was less than 0.03%. Adsorption mechanism showed that phosphate was adsorbed mainly through electrostatic force, ion-exchange, and inner-sphere surface complex. Simulated wastewater treatment experiment showed that MIL-101(Fe)/SCB3 could efficiently remove phosphate from aqueous solution.

Simultaneous removal of cationic and anionic dyes from aqueous solution by double functional groups modified bagasse.

Double functional groups modified bagasse (DFMBs), a series of new zwitterionic groups of carboxyl and amine modified adsorbents, were prepared through grafting tetraethylenepentamine (TEPA) onto the pyromellitic dianhydride (PMDA) modified bagasse using the DCC/DMAP method. DFMBs' ability to simultaneously remove basic magenta (BM, cationic dye) and Congo red (CR, anionic dye) from aqueous solution in single and binary dye systems was investigated. FTIR spectra and Zeta potential analysis results showed that PMDA and TEPA were successfully grafted onto the surface of bagasse, and the ratio of the amount of carboxyl groups and amine groups was controlled by the addition of a dosage of TEPA. Adsorption results showed that adsorption capacities of DFMBs for BM decreased while that for CR increased with the increase of the amount of TEPA in both single and binary dye systems, and BM or CR was absorbed on the modified biosorbents was mainly through electrostatic attraction and hydrogen bond. The adsorption for BM and CR could reach equilibrium within 300 min, both processes were fitted well by the pseudo-second-order kinetic model. The cationic and anionic dyes removal experiment in the binary system showed that DMFBs could be chosen as adsorbents to treat wastewater containing different ratios of cationic and anionic dyes.

Polyaminophosphoric Acid-Modified Ion-Imprinted Chitosan Aerogel with Enhanced Antimicrobial Activity for Selective La(III) Recovery and Oil/Water Separation.

In this study, polyaminophosphoric acid (PA)-functionalized ion-imprinted chitosan (CS) aerogel was fabricated for the first time, exhibiting good antibacterial property for selective La(III) recovery and oil/water separation. The as-prepared PA-CS-IIA-2 shows a remarkable adsorption capacity of 114.6 mg/g toward La(III) and high selectivity in the competitive adsorption systems, which is attributed to its abundant imprinting sites and surface functional groups. Benefiting from the amphiphilic property, the PA-CS-IIA-2 also exhibits an excellent adsorption performance for the extractant, oils, and organic solvents. Besides, the PA-CS-IIA-2 presents excellent regeneration and reusability characteristics. Moreover, compared with CS, the PA-CS-IIA-2 exhibits a significantly improved antibacterial activity originating from the PA component. Most importantly, the PA-CS-IIA-2 aerogel is capable of removing multiple pollutants all together and effectively inhibiting bacteria in the complex wastewater environments. Therefore, this study paves the way for developing high-performance rare-earth capture materials with multiple functions to meet diverse applications.

Selective capture of Pd(II) from aqueous media by ion-imprinted dendritic mesoporous silica nanoparticles and re-utilization of the spent adsorbent for Suzuki reaction in water.

The development of highly efficient adsorptive material for the selective capture of Pd(II), and re-utilization of spent Pd(II)-loaded adsorbent as an efficient catalyst for organic synthesis are of great significance, but challenging. Particularly, the heterogeneous palladium-catalyzed Suzuki reaction in aqueous media is much more challenging than that of homogeneous. Herein, several novel Pd(II) ion-imprinted polymers (PIIPs) based on dendritic fibrous silica particles are constructed by surface ion imprinting technology (SIIT), using Schiff base and pyridine groups functionalized organosilicon as functional monomer. The PIIP-3 prepared by 3 g of functional monomer exhibits the best adsorption performance, and shows ultrafast (10 min) and selective capture of Pd(II) with high uptake capacity (382.5 mg/g). Moreover, the waste Pd(II) loaded PIIP-3 (PIIP-3-Pd) can serve as a catalyst towards the Suzuki reaction in water, affording 94.2 % yield of the desired product. Interestingly, the PIIP-3-Pd can be reused 12 times without an appreciable decrease in catalytic activity, which is probably due to the imprinted cavity and specific recognition site of PIIP-3 can match and recapture Pd active species in a complex catalytic environment. Thus, this work demonstrates huge potentials of SIIT to enhance the selectivity of adsorption process and increase the lifetime of catalysts.

Decorating UiO-66-NH2 crystals on recyclable fiber bearing polyamine and amidoxime bifunctional groups via cross-linking method with good stability for highly efficient capture of U(VI) from aqueous solution.

Although polyacrylonitrile fiber (PANF) and metal-organic frameworks (MOFs) have been extensively investigated to remove U(VI) from water, their practical applications are seriously hindered by the relatively low stability of PANF in acidic solution and great difficulty of separating MOFs nanoparticles from solution, beside that, little attention is paid to the fabrication of MOFs and PANF composite materials (MPCMs) with excellent adsorption capacity for U(VI). Herein, we report the synthesis of novel MPCMs by decorating different concentrations of UiO-66-NH2 crystals onto polyamine and amidoxime groups functionalized PANF (PA-AO-PANF) through cross-linking method for U(VI) extraction. The characterization results reveal that the combination of PA-AO-PANF and UiO-66-NH2 crystals endows MPCMs with excellent separation ability, large surface area, good stability and plentiful surface functional groups, which contributes to good selectivity and enhanced adsorption performance. Consequently, the obtained UN-PA-AO-PANF-2 shows the maximum uptake capacity of 441.8 mg/g and equilibrium uptake time of 30 min towards U(VI). Besides, the U(VI) uptake ability and structure of UN-PA-AO-PANF-2 are well preserved after ten adsorption-desorption cycles. With these outstanding properties, the adsorbent has great potential for the capture of U(VI) from aqueous solutions. Importantly, this work provides a cost-effective and efficient way to construct extremely stable MPCMs hybrid fibers.

Synthesis of rice husk-based ion-imprinted polymer for selective capturing Cu(II) from aqueous solution and re-use of its waste material in Glaser coupling reaction.

With the deepening of the concept of recycling economy and green chemistry, selective capture of Cu(II) from wastewater by biosorbent and reuse of the spent Cu(II)-loaded adsorbent are of great significance. Herein, we synthesized composite of rice husk (RH) with mesoporous silica MCM-41 (RH@MCM-41) modified by organosilane containing amino and schiff groups as functional monomer and cross-linking agent. The silica modified RH@MCM-41 was employed as supporter to fabricate copper ion-imprinted polymers as absorbents (named as RM-CIIPs) via surface ion imprinting technique. Adsorption isotherms, kinetics, selectivity and mechanism of RM-CIIPs to remove Cu(II) were investigated with respect to different adsorption condition. Furthermore, we explored the catalytic activity of spent Cu(II)-loaded adsorbent in Glaser coupling reaction. Batch adsorption studies revealed that RM-CIIP-3 prepared with functional monomer shows the best adsorption capacity (91.4 mg/g) for Cu(II), and adsorption equilibrium could be reached within 30 min. RM-CIIP-3 exhibited an excellent selectivity for capturing Cu(II) and reusability in six adsorption/desorption cycles. More importantly, the spent Cu(II)-loaded adsorbent could be used as bio-heterogeneous catalyst and afford the desired product (1,4-diphenylbutadiyne) in 99.1% yield. Our research indicates an eco-friendly systematic strategy to utilize the waste material as an adsorbent for removing heavy metals and catalyst for industry.

Effects of surface modification on heavy metal adsorption performance and stability of peanut shell and its extracts of cellulose, lignin, and hemicellulose.

Effects of surface modification by carboxyl group on Pb2+ adsorption performances and stability of peanut shell and its extracts (cellulose, lignin, and hemicellulose) were investigated. Stability of the biosorbents was measured by determining organic compound release amount (TOC). Results showed that adsorption capacity of peanut shell and the extract was poor and stability of them was not good enough. Amount of organic compound released from the unmodified sorbents followed the order: cellulose > lignin > peanut shell > hemicellulose. Hemicellulose was the main organic compound release resource for the raw peanut shell. Due to the poor stability of the raw materials, peanut and its extract could not be used directly in the practical waste water treatment. After modification, adsorption capacity of peanut shell, cellulose, lignin, and hemicellulose increased by 4- to 6-folds. Stability of the modified sorbents also increased significantly, and TOC determined for the modified peanut shell, cellulose, and hemicellulose was lower than 4.0 mg L-1 in the optimum pH range from 4.0 to 6.0 even using for 30 days, which was lower than the drinking water standard in China. Modified peanut shell and its extract except for lignin could be used safely in pH ranged from 4.0 to 6.0. Surface modification could improve the adsorption performances and stability of the biosorbents.

Novel combined method of biosorption and chemical precipitation for recovery of Pb2+ from wastewater.

A novel combined biosorption-precipitation process has been designed and applied to recycle Pb2+ from low concentration lead containing wastewater. Pb2+ was firstly removed selectively from wastewater by pyromellitic dianhydride (PMDA) modified sugarcane bagasse (SB) fixed-bed column, and then, it was desorbed into the concentrated eluate and recycled by adding chemical precipitant. Adsorption performance of the column and optimum desorption and precipitation condition for Pb2+ were investigated in detail. Results showed that the as-prepared column could efficiently remove Pb2+ from aqueous solution and optimum condition for Pb2+ precipitation in eluate was at pH 3.0 and molar ratio of precipitant to Pb2+ of 5:1 by using Na3PO4 as precipitant. Recovery experiment illustrated that Pb2+ was selectively removed from wastewater containing ions of Pb2+, Zn2+, Cd2+, Ca2+, K+, and Na+ through competitive substitution adsorption on the modified SB, and mass ratio of the five metal ions in eluate was 96.8:0.7:0.7:0.7:0.5:0.5. Pb2+ in this concentrated and purified eluate solution was recycled efficiently by adding Na3PO4. The combined method had great potential in application of heavy metal recovery from wastewater.

Selective adsorption and recycle of Cu2+ from aqueous solution by modified sugarcane bagasse under dynamic condition.

Tetraethylenepentamine modified sugarcane bagasse was prepared and applied to test its feasibility in removing and recovering Cu2+ from wastewater under dynamic condition. Results showed that the Cu2+ could be selectively absorbed from wastewater by the modified SCB fixed bed column. To understand the adsorption mechanism, Cd2+ had been selected as the model interfering ion to investigate how co-ions influence the adsorption of Cu2+ on the sorbent. It was observed that the adsorption capacity of the sorbent for Cu2+ (0.26 mmol g-1) was significantly higher than that of Cd2+ (0.03 mmol g-1), even when the Cd2+ initial concentration was 100 times higher than that of Cu2+ in the binary system. This finding indicated that the presence of Cd2+ in the solution exerted negligible influence on the adsorption of Cu2+ on the modified SCB. The selectivity of the modified sorbent was further confirmed in the Cu/Cd/Mg/Pb/K quinary system. Further analysis to dynamic adsorption experiment illustrated that, due to the presence of amine groups, the modified SCB showed strong coordination ability to Cu2+, which allowed the other adsorbed ions (e.g., Cd2+) desorbed. This high adsorption selectivity toward Cu2+ suggested that this prepared sorbent would be a promising candidate for removing and recovering Cu2+ from wastewater.

Simultaneous removal of cationic and anionic dyes by the mixed sorbent of magnetic and non-magnetic modified sugarcane bagasse.

Magnetic carboxyl groups modified (MMS) and non-magnetic amine groups modified (AMS) sugarcane bagasse were prepared and mixed to remove cationic and anionic dye simultaneously from aqueous solution. For comparison, the adsorption performances of MMS, AMS and the mixed sorbent for basic magenta (cationic dye) and congo red (anionic dye) were investigated in the binary system. Zeta potential analysis showed that MMS was negatively charged and AMS was positively charged in the investigated pH range. The adsorption capacities of MMS for basic magenta and congo red were 1.24 and 0.04mmolg(-1), while those of AMS were 0.04 and 1.55mmolg(-1), respectively. Both of MMS and AMS had high adsorption capacity and affinity toward opposite-charged dye but low adsorption capacity and affinity toward similar-charged dye. Adsorption experiments in the binary system showed that only the mixed sorbent could remove the two dyes simultaneously from aqueous solution (removal efficiencies >90%). The amounts of basic magenta and congo red absorbed on the mixed sorbent both increased linearly with the increase of their initial concentrations in the investigated range. The dye loaded mixed magnetic and non-magnetic sorbents could be separated by a magnet. MMS and AMS could be regenerated by using acid and alkaline eluents, respectively. After regeneration, the MMS and AMS could be mixed again and used repeatedly. The mixed sorbent had great potential in practical dye waste water treatment.

A simple method to prepare magnetic modified beer yeast and its application for cationic dye adsorption.

The purpose of this research is to use a simple method to prepare magnetic modified biomass with good adsorption performances for cationic ions. The magnetic modified biomass was prepared by two steps: (1) preparation of pyromellitic dianhydride (PMDA) modified biomass in N, N-dimethylacetamide solution and (2) preparation of magnetic PMDA modified biomass by a situ co-precipitation method under the assistance of ultrasound irradiation in ammonia water. The adsorption potential of the as-prepared magnetic modified biomass was analyzed by using cationic dyes: methylene blue and basic magenta as model dyes. Optical micrograph and x-ray diffraction analyses showed that Fe(3)O(4) particles were precipitated on the modified biomass surface. The as-prepared biosorbent could be recycled easily by using an applied magnetic field. Titration analysis showed that the total concentration of the functional groups on the magnetic PMDA modified biomass was calculated to be 0.75 mmol g(-1) by using the first derivative method. The adsorption capacities (q(m)) of the magnetic PMDA modified biomass for methylene blue and basic magenta were 609.0 and 520.9 mg g(-1), respectively, according to the Langmuir equation. Kinetics experiment showed that adsorption could be completed within 150 min for both dyes. The desorption experiment showed that the magnetic sorbent could be used repeatedly after regeneration. The as-prepared magnetic modified sorbent had a potential in the dyeing industry wastewater treatment.

A situ co-precipitation method to prepare magnetic PMDA modified sugarcane bagasse and its application for competitive adsorption of methylene blue and basic magenta.

Magnetic pyromellitic dianhydride (PMDA) modified sugarcane bagasse (SCB) was prepared by a situ co-precipitation method. Results showed that the magnetic modified SCB could be recycled easily by an applied magnetic field. Adsorption capacities of the magnetic sorbent for cationic dyes: methylene blue and basic magenta were 315.5 and 304.9mgg(-1), respectively. Competitive adsorption in the binary system showed that concentration percentages (C(P)) and initial concentration (C(0)) both had good linear relationship with adsorption capacities of the magnetic sorbent (q(e)(')) in the investigated range. The linear equations between C(P) and q(e)(') almost did not affect by the variation of total initial concentration of the dyes (C(T)), whereas that between C(0) and q(e)(') changed greatly with it. C(P) was the main factor that impacted q(e)(') in the binary competitive adsorption system. Similar linear equations between C(P) and q(e)(') demonstrated that the magnetic sorbent had similar adsorption affinity toward the two dyes.

Desorption behavior of methylene blue on pyromellitic dianhydride modified biosorbent by a novel eluent: acid TiO2 hydrosol.

In this study, waste beer yeast powder was modified by pyromellitic dianhydride to improve its adsorption capacities for cationic dye: methylene blue (MB). According to the Langmuir equation, the maximum uptake capacities (q(m)) of the modified biomass for MB was 830.8 mg g(-1), which was about five times than that obtained on the unmodified biomass. Adsorption mechanism was investigated by FTIR. Desorption kinetics of methylene blue in six solvents: HCl (0.1 mol L(-1)), ethanol, mixtures of HCl (0.1 mol L(-1)) and ethanol with different volume ratio and a self-clean eluent: acid TiO(2) were studied in details. Results showed that desorption kinetics curve fit the two-step kinetic model, and methylene blue release process was distinctly divided into two steps: rapid and slow desorption steps. 52.2% of the methylene blue could be desorbed into TiO(2) hydrosol after 30 h desorption at the first desorption cycle, and the desorbed dye in TiO(2) hydrosol could be degrade completely under sunlight irradiation. After three desorption-photodegradation cycles, 80.0% of the absorbed dyes could be desorbed from the surface of the modified biomass. Although there was much work to do, the self-clean eluent: TiO(2) hydrosol had great potential in practical use.

Poly(amic acid)-modified biomass of baker's yeast for enhancement adsorption of methylene blue and basic magenta.

In this study, poly(amic acid)-modified biomass was prepared to improve the adsorption capacities for two cationic dyes, methylene blue and basic magenta. X-ray photoelectron spectroscopy and potentiometric titration demonstrated that a large number of imide, amine, and carboxyl groups were introduced on the biomass surface, and the concentrations of these functional groups were calculated to be 0.27, 1.08, and 1.08 mmol g(-1) by using the first derivative method. According to the Langmuir equation, the maximum uptake capacities (q(m)) for methylene blue and basic magenta were 680.3 and 353.4 mg g(-1), respectively, which were 13- and sevenfold than that obtained on the unmodified biomass. Adsorption kinetics study showed that the completion of the adsorption process needed only 40 min, which is faster than the common sorbent such as activated carbon and resin. Experimental results showed that pH and ionic strength had little effect on the capacity of the modified biomass, indicating that the modified biomass had good potential for practical use.

Polymer modified biomass of baker's yeast for enhancement adsorption of methylene blue, rhodamine B and basic magenta.

In this study, poly (methacrylic acid) modified biomass was prepared to improve the adsorption capacities for three dyes: methylene blue (MB), rhodamine B (RB) and basic magenta (BM). FTIR and potentiometric titration demonstrated that a large number of carboxyl groups were introduced on the biomass surface, and the concentration of the functional group was calculated to be 1.4 mmol g(-1) by using the first and second derivative method. According to the Langmuir equation, the maximum uptake capacities (q(m)) for MB, RB and BM were 869.6, 267.4 and 719.4 mg g(-1), which were 17-, 11- and 12-fold of that obtained on the unmodified biomass, respectively. Adsorption kinetics study showed that the completion of the adsorption process needed only 70 min, which is faster than that occur with the common sorbent such as activated carbon and resin. Temperature and ionic strength experiment showed that they both had effect on the adsorption capacity of the modified biomass. Good result was obtained when the modified biomass was used to treat dye wastewater.