Adsorption of phenolic compounds from aqueous solutions by aminated hypercrosslinked polymers

Two novel polymers （NJ-1 and N J-2） were synthesized by chemically modified a hypercrosslinked polymer NJ-0 with dimethylamine and trimethylamine, respectively. The comparison of the adsorption properties of the three polymers toward phenol, resorcin and phloroglucin was made. The study focused on the static equilibrium adsorption behaviors and the adsorption thermodynamics. Freundlich equation was found to fit the adsorption results well. The effect of amino groups introduced onto the surface of the resin and the structure of phenolic compounds on the adsorption were also studied. The hydrogen-bonding interaction and electrostatic interaction could happen between the amino groups and the adsorbates. The adsorption impetus increased as quantity of hydroxyl groups increased, but the adsorption capacity decreased due to the drop of the matching degree of the aperture of resins and the diameter of adsorbate molecules.

Binary competitive adsorption of naphthalene compounds onto an aminated hypercrosslinked macroporous polymeric adsorbent

An aminated hypercrosslinked macroporous polymeric adsorbent was synthesized and characterized. Adsorption isotherms for 1 amino 2 naphthol 4 sulfonic acid(1, 2, 4 acid) and 2 naphthol obtained from various binary adsorption environments can be well fitted by Freundlich equation, which indicated a favorable adsorption process in the studied range. Adsorption for 1, 2, 4 acid was an endothermic process in comparison with that for 2 naphthol of an exothermic process. 2 naphthol molecules put a little influence on the adsorption capacity for 1, 2, 4 acid. However, the adsorption to 1, 2, 4 acid depressed that to 2 naphthol in a large extent for the stronger electrostatic interaction between 1, 2, 4 acid and adsorbent. The predominant mechanism can be contributed to the competition for adsorption sites. And the simultaneous environment was confirmed to be helpful to the selective adsorption towards 1,2,4 acid based on the larger selectivity index.

ADSORPTION OF CHLOROFORM AND TRICHLOROETHYLENE IN WATER WITH A NEW KIND OF HYPERCROSSLINKED RESINS

In this paper two newly developed hypercrosslinked resins were used to treat micropolluted drinking water and their static and kinetic adsorption were investigated at 293 K. The results show that these two adsorbents are superior to Amberlite XAD-4 for removing chloroform and trichloroethylene in aqueous solutions. The breakthrough capacity and the total capacities from mini-column adsorption studies for chloroform and trichloroethylene on XAD-4, ZH-01 and ZH-00 are calculated respectively under experimental conditions

Synthesis and application of a hydrophobic hypercrosslinked polymeric resin for removing VOCs from humid gas stream

A hydrophobic hypercrosslinked polymeric resin LC-1 was prepared and characterized. The properties of LC-1 resin were compared with those of a commercial hypercrosstinked polymer NDA-201 resin. In addition, the dynamic adsorption of trichloroethylene （TCE） onto LC-1 under dry and humid conditions at 303 K was investigated, the result shows that LC-1 possesses high hydrophobic property and can remove TCE from gas stream without effect of high humidity efficiently.

PROPERTIES AND THERMODYNAMICS OF ADSORPTION OF BENZOIC ACID ONTO XAD-4 AND A WATER-COMPATIBLE HYPERCROSSLINKED ADSORBENT

The adsorption behavior of benzoic acid onto a water-compatible hypercrosslinked polymeric adsorbent NJ-8 wascompared with that onto macroporous Amberlite XAN-4. This paper focuses on the static equilibrium adsorption behaviors,the adsorption thermodynamics and the column dynamic adsorption profiles. Five isotherm models are used to fit the results.This shows that the Freundlich equation can give a perfect fit. The specific surface area of NJ-8 is about as high as that ofAmberlite XAD-4, but the adsorbing capacity for benzoic acid on NJ-8 is about 14.9%-64.8% higher than that on AmberliteXAD-4, which is attributed to its microporous mechanism and partial polarity. The negative values of the adsorptionenthalpy are indicative of an exothermic process. Both enthalpy and free energy changes of adsorption manifest a physicalsorption process. The negative values of the adsorption entropy indicate that adsorption is well consistent with the restrictedmobilities and the configurations of the adsorbed molecules on the surface of the studied adsorbents with superficialheterogeneity. Both adsorbents were used in mini-column experiments to demonstrate the higher breakthrough adsorbing capacity of the hypercrosslinked polymeric adsorbent NJ-8 to benzoic acid, as compared with that of Amberlite XAD-4.

Facile synthesis and characterization of novel pseudo-hypercrosslinked resin

A kind of pseudo-hypercrosslinked polymer resin was firstly synthesized via a continuous Friedel-Crafts alkylation poly- merization of benzene, diphenyl and their dichloromethyl derivatives. And the micromorphology and adsorption properties of these resins were investigated. The results demonstrated that the novel resins have high-specific surface area （581.26-974.88 m^2/g）, high- pore volume （0.56-1.65 mL/g）, small average porous radius （1.93-3.67 nm） and excellent adsorption properties for small non-polar organic molecules.

ADSORPTION OF 2,4-DICHLOROBENZOXYACETIC ACID ONTO HYPERCROSSLINKED RESIN MODIFIED BY PHENOLIC HYDROXYL GROUP (AM-1)

An experimental comparison of the adsorption properties of hypercrosslinked resin AM-1 modified by phenolic hydroxyl group with Amberlite XAD-4 toward 2,4-dichlorobenzoxyacetic acid was performed. This paper focuses on the static equilibrium adsorption behaviors and the adsorption thermodynamics. Two isotherm models were used to explain the results. It is seen that the Langmuir equation can give a perfect fit. The adsorption capacities from the different ranges of temperature, the adsorption enthalpy change value and the comparison of desorption conditions lead to the same conclusion that the adsorption of 2,4-dichlorobenzoxyacetic acid from water onto AM-1 is a type of physical and chemical transition.

ADSORPTION CHARACTERISTICS OF CHLOROPHENOLS FROM AQUATIC SYSTEMS BY HYPERCROSSLINKED RESINS MODIFIED WITH BENZOYL GROUP

A hypercrosslinked polymeric adsorbent （ZH-03） for adsorbing and removing chlorophenolic compounds from their aqueous solutions was studied, including the static adsorption. The equilibrium adsorption data were fit to Freundlich adsorption isothermic models to evaluate the model parameters. Thermodynamic studies on the adsorption of chlorophenolic compounds on ZH-03 indicated that there were chemisorption transitions for 2,4,6-trichlorophenol and physical adsorption processes for 2-chlorophenol and 2,6-chlorophenol, and ZH-03 showed the homogeneous nature of the adsorbent surface. Column adsorption for chlorophenols wastewater shows the advantages of the ZH-03 adsorbent for adsorbing the following chlorophenolic compounds as 2-chlorophenol, 2,6-dichlorophenol and 2,4,6-trichlorophenol. Sodium hydroxide was used for desorpting chlorophenols from ZH-03 and showed excellent performance.

Adsorption mechanism of phenolic compounds from aqueous solution on hypercrosslinked polymeric adsorbent

The adsorption of two phenols, namely, phenol and salicylic acid(SA) onto a water-compatible hypercrosslinked polymeric resin(NJ-8) were studied in terms of pseudo-second-order and first order mechanisms for chemical sorption as well as an intraparticle diffusion mechanism process. Kinetic analysis showed that the intraparticle diffusion process was the essential rate-controlling step. The activation energies of sorption have also been evaluated with the pseudo-second-order and intraparticle diffusion constants, respectively. Adsorption equilibrium data were well fitted by the Langmuir, Freundlich and Redlich-Peterson isotherms. Adsorption was exothermic and basically of a type of transition between physical and chemical character. The sorption capacity was higher for SA due to its more hydrophobic. Phenol has a higher adsorption enthalpy since it could form stronger hydrogen bonding on NJ-8.

THERMODYNAMIC STUDY OF ADSORPTION OF PHENOLIC COMPOUNDS FROM AQUEOUS SOLUTION BY A WATER-COMPATIBLE HYPERCROSSLINKED POLYMERIC ADSORBENT

Equilibrium data for the adsorption of phenolic compounds, i.e., phenol, p-cresol, p-chlorophenol and p- nitrophenol from aqueous solutions by a water-compatible hypercrosslinked polymeric adsorbent (NJ-8) within temperature range of 283-323 K were obtained and correlated with a Freundlich-type of isotherm equation, so that equilibrium constants KF and n were obtained. The capacities of equilibrium adsorption for all the four phenolic compounds on the NJ-8 from aqueous solutions are around 2 times as high as those of Amberlite XAD-4, which may be attributed to the unusual micropore structure and the partial polarity on the network. The values of the enthalpy (always negative) are indicative of an exothermic process, which manifests the adsorption of all the four phenolic compounds on the two polymeric adsorbents to be a process of physical adsorption. The negative values of free energy change show that the solute is more concentrated on the adsorbent than in the bulk solution. The absolute free energy values of adsorption for NJ-8 are always higher than those for Amberlite XAD-4, which indicates that phenolic compounds are preferentially adsorbed on NJ-8. The negative values of the adsorption entropy are consistent with the restricted mobilities of adsorbed molecules of phenolic compounds as compared with the molecules in solution. The adsorption entropy values of phenolic compounds for NJ-8 are lower than those for Amberlite XAD-4, which means the micropores of NJ-8 require more orderly arranged adsorbate.

A fibrous hypercrosslinked sorbent prepared on PP-ST-DVB matrix via post-crosslinking reaction

A fibrous sorbent possessing abundant micropore structure was firstly prepared via post-crosslinking reaction on the PP-ST-DVB original fiber. Its micromorphology and sorptive properties were investigated, and the results demonstrated that the novel fibrous hypererosslinked sorbent has narrow pore-size distribution, small average porous radius （1.90 nm）, high specific surface area （362.31 m^2/g）, and fine sorptive properties for small organic molecules.

ADSORPTION OF 2,4-D ON MODIFIED HYPERCROSSLINKED POLYSTYRENE(NDA-99)AND XAD-4 RESIN

The adsorption behavior of pesticide 2,4-dichlorophenoxyacetic acid(2,4-D)in aqueous solution has been investigated using a hypercrosslinked polystyrene adsorbent(NDA-99)modified by dimethylamine group as well as a nonionic macroporous adsorbent(XAD-4).The Langmuir and Freundlich isotherm models were employed to fit the experimental data to describe adsorption mechanism.It shows that NDA-99 resin exhibits an adsorption affinity for 2,4-D higher than XAD-4 resin owing to its exceptional micropore structure and the amine group of the hypercrosslinked matrix. Further studies indicate that the hydrogen bonding interaction and the stronger π-π conjugation play a significant role in the course of the adsorption of 2,4-D on NDA-99 resin,which is in agreement with the IR spectroscopic results and the ΔE values of HOMO(the highest occupied molecular orbit)of adsorbent and LUMO(the lowest unoccupied molecular orbit)of adsorbate calculated from the MINDO/3 model.

Adsorption of catechol from aqueous solution by aminated hypercrosslinked polymers

Adsorption of catechol from aqueous solution with the hypercrosslinked polymeric adsorbent NDA-100 and its derivatives AH-1, AH-2 and AH-3 aminated by dimethylamine, the commercial resin Amberlite XAD-4 and weakly basic anion exchanger resin D301 was compared. It was found that the aminated hypercrosslinked resins had the highest adsorption capacities among the tested polymers. The empirical Freundlich equation was successfully employed to describe the adsorption process. Specific surface area and micropore structure of the adsorbent, in company with tertiary amino groups on matrix affected the adsorption performance towards catechol. In addition, thermodynamic study was carried out to interpret the adsorption mechanism. Kinetic study testified that the tertiary amino groups on the polymer matrix could decrease the adsorption rate and increase the adsorption apparent activation energy.

Efficient recovery of aromatic compounds from the wastewater of styrene monomer and propylene oxide co-production plant via hypercrosslinked aryl-rich starch-β-cyclodextrin polymeric sorbent

Adsorptive recovery of valuable components from industrial wastewater is highly desirable for avoiding resource wastage but remains a challenge.Herein,we develop an efficient continuous adsorption process for recovering aromatic compounds in wastewater from styrene monomer and propylene oxide coproduction(SMPO)plant.Based on our insight into the potential of bio-based porous materials for adsorption application,starch-graft-polystyrene(SPS)and aryl-modifiedβ-cyclodextrin(ACD)were prepared,and novel hypercrosslinked porous polymers combined SPS with ACD(HSPS-ACDs)were synthesized through external crosslinking approach.In a binary-component system,the best-performing one HSPS-ACD(H)with high ACD content and large specific surface area possessed superior capacities for the representative aromatic compounds,acetophenone(AP,2.81 mmol·g^(-1))and 1-phenylethanol(1-PE,1.35 mmol·g^(-1))compared with the previously reported materials.Further,the adsorption properties of aromatic compounds on HSPS-ACD(H)were investigated in batch mode.For practical application,continuous adsorption experiments were conducted in a HSPS-ACD(H)-packed fixed bed,where the target aromatic components in wastewater were effectively retained and further released by elution.Besides showing the reversible adsorption and efficient enrichment effect,the HSPS-ACD(H)-packed fixed bed also maintained great stability in multiple cycles.Moreover,quantum chemical calculations were performed to elucidate the potential mechanism of adsorption of AP and 1-PE onto HSPS-ACD(H).

ADSORPTION OF PHENOL AND NITROPHENOLS ON A HYPERCROSSLINKED POLYMERIC ADSORBENT

The adsorption of phenol and nitrophenols on hypercrosslinked polymeric adsorbent was studied as a function of the solution concentration and temperature. Adsorption isotherms of phenol and nitrophenols on hypercrosslinked resin were determined. These isotherms were modeled according to the Freundlich adsorption isotherm. The isotherms for phenol and nitrophenols on hypercrosslinked resin were assigned as L curves. Thermodynamic parameters were calculated for all phenol and nitrophenols. The kinetics experiment results showed that the adsorption rates were of the first-order kinetics. The rate constants at 303K were calculated.

EFFECT OF HYPERCROSSLINKED RESINS SURFACE CHEMISTRY ON THE ADSORPTION OF PHENOL FROM AQUEOUS SOLUTION

Two hypercrosslinked resins with similar physical characters but different surface chemistry were synthesized and used to remove phenol from aqueous solutions. The FTIR spectra, elemental analysis and the Boehm titration were used to characterize the chemical properties of the resins. The adsorption experiments were carried out using the bottle-point technique, and the effects of the surface chemistry on the adsorption were discussed. The adsorption data fit well with the Freundlich model, indicating the heterogeneity of the resins surface. It could be seen from the experimental results that the adsorption capacity increased with the increase in the total surface concentration of oxygen-containing groups. The pH dependence and the effects of ionic strength were also discussed. The kinetic adsorption data fit well with the pseudo-second order model, and the results showed that the surface oxygen-containing groups have little effect on the adsorption rate.

SINGLE AND BINARY ADSORPTION PERFORMANCE OF SALICYLIC ACID AND 5-SULFOSALICYLIC ACID ONTO HYPERCROSSLINKED POLYMERIC ADSORBENTS

Single and binary adsorption behaviors of salicylic acid and 5-sulfosalicylic acid onto hypercrosslinked polymeric adsorbents,i.e.NDA-101 and NDA-99 were investigated.The Freundlich model can successfully describe all the adsorption isotherms tested,which indicates a favorable and exothermic adsorption process.The adsorption of salicylic acid relies on π-π interaction,while the electrostatic interaction further influences the adsorption of 5-sulfosalicylic acid onto NDA-99.The adsorptive capacity of salicylic acid on NDA-99 decreases but increases on NDA-101 with 5-sulfosalicylic acid as the background component in a binary solute system.The amount of 5-sulfosalicylic acid adsorbed was decreased with the increase in initial concentration of salicylic acid on both adsorbents.The competition for the adsorption sites is considered to be predominant in the solid-to-liquid interaction process.The adsorption selectivity of salicylic acid onto NDA-101 is higher than onto NDA-99 by more than an order of magnitude.Thus,combination technique involving NDA-101 followed by NDA-99 can be effectively applied to separate and recover salicylic acid and 5-sulfosalicylic acid from wastewater.

Two Organic Phase Suspension Polymerization for Novel Hypercrosslinked Resin Bead by Polycondensation of CMB

The suspension polymerization with two organic phases was adopted to prepare spherical hyper- crosslinked resin by self-polycondensation of 4,4＇-bis-（chloromethyl）- 1, 1＇-biphenyl （CMB）. The chemical structure,morphology and pore characteristics of the novel spherical resin were characterized with Fourier transform infrared spectroscopy （FTIR）, micrograph and Brunauer-Emmett-Teller （BET）. It is found that the suspension system and stirring speed impose a great influence upon the regularity and size distribution of hypercrosslinked beads. To prepare CMB resin beads with diameter of about 300 μm, the optimal condition is as follows： stirring speed 300 r·min^-1, and the volume ratio of the two organic phases （nitrobenzene/dimethyl silicon oil） 1 ： 5. After the self-polycondensation and sqccedent post-crosslinking of CMB monomer, the spherical adsorbent presents high spec^al surface area （1190 m^2· g^-1） and abundant pore^volume （0.714 cm^3· g^-1）, and could be potentially applied qn the adsorption of various organic molecules and synthesis of porous ion exchanger.

STUDY ON SIDE REACTION IN THE SYNTHESIS OF HYPERCROSSLINKED POLYMERS

The systematical study about side reactions have revealed the formation mechanism of oxygen-containing groups of hypercrosslinked polymers. Surface chemistry and functionality of the polymers are characterized by Fourier-transform infrared spectroscopy (FT-IR), solid state nuclear magnetic resonance (NMR) and contact angle. The results showed that the ether groups were from chloromethylated reaction, and the alcohol groups arose from partial hydrolysis of chloromethyl groups during the post-crosslinking reaction, and the carbonyl functionality was formed by further oxidation of the alcohol groups. Catalyst and solvent used in the postcrosslinking reaction would greatly influence the surface chemistry of the polymer.

TREATMENT OF SORBIC ACID MANUFACTURING WASTEWATER BY HYPERCROSSLINKED POLYMERIC ADSORBENT (NDA-150)

The treatment of sorbic acid manufacturing wastewater by NDA-150 resin was investigated. The experiments show that this process is suitable for the treatment of sorbic acid manufacturing wastewater. About 98% sorbic acid and 50% CODcr were removed under optimal operating conditions, and 70% of sorbic acid in sorbic acid manufacturing wastewater was reclaimed. This process makes it possible to recover valuable materials from the wastewater and to improve the quality of effluent water.