Investigation of selected textile colors and heavy metals removal from waste water using aminofunctionalized macroporous polymers based on glycidyl methacrylate

Cilj ove doktorske disertacije je ispitivanje mogućnosti praktične primjene umreženih makroporoznih amino-funkcionalizovanih kopolimera na bazi glicidilmetakrilata (GMA) kao sorbenta za uklanjanje različitih zagađujućih supstanci iz vodenih rastvora. Postupkom suspenzione kopolimerizacije su sintetisana dva osnovna uzorka kopolimera glicidilmetakrilata i etilenglikoldimetakrilata (EGDMA), skraćeno: PGME. Modifikacijom osnovnih uzoraka kopolimera u reakcijama sa etilendiaminom (eda), dietilentriaminom (deta) i trietilentetraminom (teta), dobijeni su uzorci amino-funkcionalizovanih kopolimera: PGME-en, PGME-deta i PGME-teta. Određen je elementarni sastav osnovnih i amino-funkcionalizovanih uzoraka umreženih makroporoznih PGME mikroanalizom, a zatim su okarakterisani infracrvenom spektroskopijom sa Furijeovom transformacijom (FTIR). Osnovni parametri poroznosti sintetisanih kopolimera - specifična zapremina pora, Vs, i prečnik pora koji odgovara polovini zapremine pora, DV/2, određeni su metodom živine porozimetrije i pomoću tih vrijednosti je izračunata specifična površina pora, SHg. U eksperimentima sorpcije odabranih zagađujućih supstanci ispitivana je efikasnost uklanjanja sintetičkih tekstilnih boja, teških metala i radionuklida iz vodenih rastvora. Uzorak PGME-deta je izabran za ispitivanje sorpcije kisele boje Acid Orange 10 (AO10) i reaktivne boje Reactive Black 5 (RB5). Ispitan je uticaj mase sorbenta i pH vrijednosti rastvora boje na efikasnost sorpcije obe boje, kao i uticaj režima miješanja, da bi se odredili optimalni eksperimentalni uslovi. Zavisnost brzine sorpcije od koncentracije rastvora boje za AO10 je ispitivana u opsegu od 20-70 mg dm-3, a za RB5 u opsegu od 30-150 mg dm-3. Dobijeni kapaciteti sorpcije su bili osnova za proučavanje kinetičkih i difuzionih modela sorpcije odabranih sintetičkih boja, takođe i adsorpcionih izotermi. Da bi se ispitao mehanizam procesa sorpcije primjenjeni su modeli pseudoprvog i pseudo-drugog reda, model unutarčestične difuzije i Mek Kejev model. Za analizu sorpcione ravnoteže korišćeni su Langmirov i Frojndlihov model izoterme. Selektivnost kopolimernog sorbenta je ispitivana iz binarnih rastvora boja AO10 i Bemacid Gelb, kao i AO10 i Bezaktiv Rot, a upoređena je efikasnost sorpcije boje AO10 na aktivnom uglju i PGME-deta. Uticaj temperature rastvora boje na kapacitet sorpcije je ispitana na četiri različite temperature za tri različite koncentracije RB5. Sorpcija šestovalentnog hroma je ispitivana pomoću PGME-deta iz jednokomponentnih vodenih rastvora različitih koncentracija, binarnih rastvora jona hroma i bakra, kao i višekomponentne smješe jona hroma, bakra, kobalta i kadmijuma. Upoređena je brzina sorpcije Cr(VI), Cu(II), Co(II) i Cd(II) jona, izračunati kapaciteti sorpcije i dobijeni rezultati analizirani primenom modela pseudo-prvog i pseudo-drugog reda, kao i modela unutarčestične difuzije. Radi detaljnije analize uticaja pH vrijednosti na sorpciju metalnih jona pomoću PGME-deta u vodenom rastvoru izvedeni su eksperimenti sorpcije Cu(II) i Cd(II) jona bakra pri pH=4 i sorpcije Pb(II) jona, pri pH=2, na PGME-deta. Određeni su kapaciteti sorpcije, a zatim analizorani modelom pseudo-prvog i pseudo-drugog reda, kao i modelom unutarčestične difuzije. Uzorci kopolimera sa vezanim metalnim jonima su analizirani infracrvenom spektroskopijom (FTIR), snimljeni skenirajućom elektronskom mikroskopijom sa energetsko disperzivnom spektroskopijom x-zraka (SEM/EDX), a rendgenska fotoelektronska spektroskopija (XPS) je urađena da bi se otkrile promjene elementarnog hemijskog sastava osnovnog kopolimera i prisustvo funkcionalnih grupa na površini modifikovanog uzorka PGME-deta. Spektar visoke rezolucije (HRES) za C1s, N1s, Cd3d, Cu2p i Pb4f je snimljen da bi se ispitale interakcije između jona metala i amino grupa. Vodeni rastvori pertenetatnog jona, 99mTcO4 -, su korišteni za uklanjanje radionuklida pomoću dva amino-funkcionalizovana uzorka kopolimera, PGME-en i PGME-teta. Ispitivan je uticaj pH vrijednosti na kapacitet sorpcije izotopa 99mTc, a za analizu dobijenih rezultata su upotrebljeni modeli pseudo-prvog i pseudodrugog reda.The goal of this doctoral dissertation was to investigate the possibility of practical application of macroporous crosslinked amino-functionalized copolymers based on glycidyl methacrylate (GMA) as a sorbent for the removal of various pollutants from aqueous solutions. Two initial samples of copolymer glycidyl methacrylate and ethylene glycol (EGDMA) - abbreviated: PGME, were synthesized by suspension copolymerization. By modification of the basic copolymer samples in reactions with ethylene diamine (eda), diethylenetriamine (deta) and triethylenetetramine (teta), the samples of amino-functionalized copolymers were prepared: PGME-en , PGME-deta and PGME-teta. The elemental composition of initial crosslinked macroporous PGME and amino-functionalized samples was determined by miceoanalysis, and the samples were further characterized by Fourier transform infrared spectroscopy (FTIR). The porosity parameters of copolymers - specific pore volume, Vs, and the pore diameter corresponding to half the pore volume, DV/2, were determined by mercury porosimetry and specific surface of pores, SHg, was calculated by using these values. The removing efficiency of selected pollutants from aqueous solutions, such as synthetic textile dye, heavy metals and radionuclide, was investigated by sorption experiments. Sample PGME-deta was selected for testing the sorption of acidic dye Acid Orange 10 (AO10) and reactive dye Reactive Black 5 (RB5). The influence of the mass of absorbent and pH value of the dye solution on the sorption efficiency of both dyes and the effect of mixing regimes was investigated in order to determine optimal experimental conditions. The dependence of the sorption rate on the concentration of the dye solution for AO10 is examined in the range of 20-70 mg dm-3 and for RB5 in the range of 30-150 mg dm-3. The obtained sorption capacities for selected synthetic dyes were the basis for kinetic analysis with kinetics and diffusion sorption models, as well as adsorption isotherms. Models of Pseudo-first-order (PFO) pseudo-second-order (PSO), intraparticle diffusion (IPD) and Mc Key models were applied for the sorption mechanism investigation.Langmuir and Freundlich model isotherms were used for the analysis of sorption equilibrium. Selectivity of copolymer sorbent is studied from the binary solutions, AO10-Bemacid Gelb and AO10-Bezaktiv Rot. The sorbent efficiency of active coal and PGME-deta for AO10 sorption were compared. The influence of dye solution temperature on the sorption capacity was examined at four different temperatures for three different concentrations of RB5. The sorption of hexavalent chromium was studied using PGME-deta from one-component aqueous solutions of different concentrations, binary solution chromium and copper ions, and multicomponent mixtures of chromium, copper, cobalt and cadmium ions. The rate of sorption of Cr(VI), Cu(II), Co(II) and Cd(II) ions were compared and calculated sorption capacities were tested by using PFO, PSO and IPD models. For the purpose of more detailed analysis of the pH influence on the metal ions sorption of the sorbent PGME-deta in an aqueous solution, the sorption experiments were performed for Cu(II) and Cd(II) ions at a pH=4 and the sorption of Pb(II) ions at pH=2. The sorption capacities were calculated, and tested with PFO and PSO models, as well as the intraparticle diffusion model. Copolymer samples with bound metal ions were analyzed by Fourier transform infrared spectroscopy (FTIR), and scanning energy-dispersive X-ray spectroscopy (SEM/EDX). X-ray photoelectron spectroscopy XPS analysis was performed to detect changes in elemental chemical composition of the initial copolymers and the presence of functional groups on the surface of modified samples PGME-deta. The high resolution spectrum (HRES) for C1s, N1s, Cd3d, Cu2p and Pb4f was made to characterize the interaction between the metal ions and amino groups. Removal of radionuclides from aqueous solutions and the pH effect on the sorption capacity of the isotope 99mTc was studied by sorption of pertechnetate ions (99mTcO4 -) onto two copolymer samples: PGME-en and PGME-teta. The obtained results were analyzed by PFO and PFO models

Funkcionalizovani makroporozni kopolimer na bazi glicidilmetakrilata - uticaj liganda i parametara poroznosti na sorpciju Cu(II) jona iz vodenih rastvora

The removal of heavy metals from hydro-metallurgical and other industries' wastewaters, their safe storage and possible recovery from waste- water streams is one of the greater ecological problems of modern society. Conventional methods, like precipitation, adsorption and biosorption, electrowinning, membrane separation, solvent extraction and ion exchange are often ineffective, expensive and can generate secondary pollution. On the other hand, chelating polymers, consisting of crosslinked copolymers as a solid support and functional group (ligand), are capable of selectively loading different metal ions from aqueous solutions. In the relatively simple process, the chelating copolymer is contacted with the contaminated solution, loaded with metal ions, and stripped with the appropriate eluent. Important properties of chelating polymers are high capacity, high selectivity and fast kinetics combined with mechanical stability and chemical inertness. Macroporous hydrophilic copolymers of glycidyl methacrylate and ethylene glycol dimethacrylate modified by different amines show outstanding efficiency and selectivity for the sorption of precious and heavy metals from aqueous solutions. In this study poly(GMA-co-EGDMA) copolymers were synthesized with different porosity parameters and functionalized in reactions with ethylene diamine (EDA), diethylene triamine (DETA) and triethylene tetramine (TETA). Under non-competitive conditions, in batch experiments at room temperature, the rate of sorption of Cu(II) ions from aqueous solutions and the influence of pH on it was determined for four samples of amino-functionalized poly(GMA-co-EGDMA). The sorption of Cu(II) for both amino-functionalized samples was found to be very rapid. The sorption half time, t1/2, defined as the time required to reach 50% of the total sorption capacity, was between 1 and 2 min. The maximum sorption capacity for copper (2.80 mmol/g) was obtained on SGE-10/12-deta sample. The sorption capacity of Cu(II) ions increases with increasing pH and has maximum at pH ~5. In the experimental pH range, the maximum sorption capacity of Cu(II) ions again is reached on SGE-10/12-deta. By comparing literature data and obtained results it is possible to conclude that amino-functionalized macroporous copolymers based on glycidyl methacrylate are efficient for sorption of Cu(II) ions from aqueous solutions and sorption capacity for copper mostly depends on type of amine with which the basic copolymer is functionalized.Makroporozni hidrofilni kopolimeri glicidilmetakrilata i etilenglikoldimetakrilata modifikovani različitim aminima poseduju izraženu efikasnost i selektivnost pri sorpciji plemenitih i teških metala iz vodenih rastvora. U ovom radu su sintetisani uzorci poli( GMA-co-EGDMA) sa različitom poroznošću i funkcionalizovani reakcijama sa etilendiaminom, dietilentriaminom i trietilentetraminom. Pri nekompetitivnim uslovima je, šaržnom metodom na sobnoj temperaturi, određena brzina sorpcije Cu(II) jona iz vodenih rastvora na četiri uzorka amino-funkcionalizovanog kopolimera, kao i uticaj pH. Pokazalo se da je sorpcija Cu(II) jona veoma brza, sa poluvremenom sorpcije ? 2 min, kao i da se sa povećanjem pH kapacitet sorpcije Cu(II) povećava i maksimalan je na ~pH 5

Study of copper adsorption on aminofunctionalized macroporous poly(gma-co-egdma)

Macroporous crosslinked copolymer of glycidyl methacrylate and ethylene glycoldimethacrylate (PGME) was synthesized by suspension copolymerisation and modified by ring-opening reaction of epoxy groups with ethylene diamine, diethylene triamine and triethylene tetramine. The uptake of copper ions by amino-functionalized macroporous PGME from aqueous solutions was investigated in batch experiments. The equilibrium data fitted well with the Langmuir model.Physical chemistry 2006 : 8th international conference on fundamental and applied aspects of physical chemistry; Belgrade (Serbia); 26-29 September 200

Analysis of hexavalent chromium sorption on macroporous copolymer grafted with hexamethylene diamine

In this study, macroporous glycidyl methacrylate based copolymers with different crosslinking degree and porosity parameters, functionalized with hexamethylene diamine were tested for Cr(VI) sorption.[http://savremenimaterijali.info/sajt/doc/file/SM2013/SM2013_KNJIGA_APSTRAKATA.pdf

Kinetic study of pentavalent vanadium sorption on magnetic macroporous copolymer of glycidyl methacrylate

Chelating copolymers show high efficiency in sorption of different ionic species in aqueous solutions. The specific structure of chelating macroporous copolymers made by the porous matrix and functional groups with the heteroatoms N, O, S and P; allows them to establish various types of interactions with ions and molecules from the immediate surroundings. Furthermore amino-functionalized macroporous copolymer of glycidyl methacrylate and ethylene glycol dimethacrylate poli (GME) has a high capacity and good selectivity for the precious and heavy metal ions over alkali and alkaline earth metals. In this study, aminofunctionalized magnetic macroporous m-poli (GME)-deta was fully characterized in terms of its structural properties using: FTIR, SEM/EDX and XRD analysis. The macroporous copolymer was further used to investigate the sorption of pentavalent vanadium oxyanions from diluted aqueous solutions (Ci = 25 ppm) in a batch system, at room temperature (298 K). The oxyanion concentrations in a solution was determined by inductively coupled plasma atomic emission spectroscopy (ICP-AES).The pseudo-first-order (PFO), pseudo-second-order (PSO), Elovich and intra-particle diffusion (IPD) models were used to analyze the kinetic data. The study has shown that sorption is rapid, i.e. the half-sorption time, t1/2 is approximately 1 minute. Initially, it has been the dominant sorption on the surface of the particles and the process has been best described by the PSO model (which takes into account the binding between sorbate and sorbent). The moment it has reached saturation of the sorbents surface active sites, sorption rate decreases significantly because the sorption has been limited by the rate of diffusion through the pores and kinetic has been controlled by the intraparticle diffusion process. IPD kinetic model showed a good fit to the experimental data with R2 values > 0.95

Kinetics of hexavalent chromium sorption on amino-functionalized macroporous glycidyl methacrylate copolymer

Two samples of macroporous crosslinked poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate), poly(GMA-co-EGDMA), with different porosity parameters were synthesized by suspension copolymerization and functionalized with ethylene diamine and diethylene triamine. The kinetics of Cr(VI) sorption by amino-functionalized poly(GMA-co-EGDMA) was investigated under non-competitive conditions. Competitive kinetics was studied from following multicomponent solutions: Cu(II) and Cr(VI); Cu(II), Co(II), Cd(II) and Ni(II): Cr(VI), Cu(II), Co(II) and Cd(II) solutions. Two kinetic models (the pseudo-first and pseudo-second-order) were used to determine the best-fit equation for the metals sorption by poly(GMA-co-EGDMA)-en and poly(GMA-co-EGDMA)-deta

Macroporous and non-porous amino-functionalized glycidyl methacrylate based copolymers for hexavalent chromium sorption

Two porous samples and one non-porous sample of crosslinked poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) [abbreviated PGME] were synthesized by suspension copolymerization and functionalized by ring-opening reaction of the pendant epoxy groups with diethylene triamine (deta). Initial PGME, as well as amino-functionalized samples, were characterized by FT-IR spectroscopy, mercury porosimetry, scanning electron microsopy and elemental analysis. The kinetics of Cr(VI) sorption by amino-functionalized PGME was investigated in batch experiments under non-competitive conditions. It was found that the porosity of PGME-deta samples plays an important role in Cr(VI) uptake. Cr(VI) sorption by macroporous amino-functionalized samples was rapid, with the uptake capacity higher than 80% after 30 minutes. Two kinetic models (the pseudo-first and the pseudo-second order) were used to determine the best-fit equation for chromium(VI) sorption by PGME-deta

Macroporous and non-porous amino-functionalized glycidyl methacrylate based copolymers for hexavalent chromium sorption

Two porous samples and one non-porous sample of crosslinked poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) [abbreviated PGME] were synthesized by suspension copolymerization and functionalized by ring-opening reaction of the pendant epoxy groups with diethylene triamine (deta). Initial PGME, as well as amino-functionalized samples, were characterized by FT-IR spectroscopy, mercury porosimetry, scanning electron microsopy and elemental analysis. The kinetics of Cr(VI) sorption by amino-functionalized PGME was investigated in batch experiments under non-competitive conditions. It was found that the porosity of PGME-deta samples plays an important role in Cr(VI) uptake. Cr(VI) sorption by macroporous amino-functionalized samples was rapid, with the uptake capacity higher than 80% after 30 minutes. Two kinetic models (the pseudo-first and the pseudo-second order) were used to determine the best-fit equation for chromium(VI) sorption by PGME-deta

Cu(II) immobilization onto a one-step synthesized poly(4-vinylpyridine-co-ethylene glycol dimethacrylate) resin: Kinetics and XPS analysis

Synthesis of an unconventional resin based on 4-vinylpyridine (4-VP) and its Cu(II) sorption behavior were studied. Three samples of macroporous crosslinked poly(4-vinylpyridine-co-ethylene glycol dimethacrylate) (P4VPE) with different porosity parameters were prepared by suspension copolymerization by varying the n-heptane amount in the inert component. The samples were characterized by mercury porosimetry, elemental analysis and X-ray photoelectron spectroscopy (XPS). The sorption of P4VPE for Cu(II) ions, determined under non-competitive conditions, was relatively rapid, i.e., the maximum capacity was reached within 30 min. The maximum experimental sorption capacity for the sample with the highest values of pore diameter and specific pore volume (sample 3, Q(eq) = 89 mg g(-1)) was 17.5 times higher than for the sample with the lowest values of pore diameter and specific pore volume (sample 1, Q(eq) = 5.1 mg g(-1)). Since the values for pyridine content in all P4VPE samples were almost the same, it was concluded that the porosity parameters have predominant influence on Cu(II) sorption rates on P4VPE. The sorption behavior and the rate-controlling mechanisms were analyzed using six kinetic models (pseudo-first order, pseudo-second order, Elovich, intraparticle diffusion, Bangham and Boyd models). XPS study clarified the nature of the formed P4VPE-Cu(II) species

Non-linear kinetic isotherms and thermodynamic behavior of As(V) onto hybrid nanocomposite

Kinetic, equilibrium and thermodynamic of arsenate sorption onto magnetic polymer sorbent based on glycidyl methacrylate were investigated. The maximum sorption capacity of 0.59 mg/g was obtained. The experimental data were analyzed by seven kinetic models and eight isotherm models. Nonlinear regression method was used to fit the data to the kinetic and isotherm models. Thus, two error functions; coefficient of determination and Chi-square statistic test were applied to evaluate the sorption data. It was shown that arsenate sorption obeys the pseudo-second-order model with evident influence of pore and film diffusion. The Freundlich and all three-parameter isotherm models proved to be the best representatives of arsenate sorption. Thermodynamic studies implied endothermic and spontaneous process in nature