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 primjeneumreženih makroporoznih amino-funkcionalizovanih kopolimera na baziglicidilmetakrilata (GMA) kao sorbenta za uklanjanje različitih zagađujućihsupstanci iz vodenih rastvora.Postupkom suspenzione kopolimerizacije su sintetisana dva osnovnauzorka kopolimera glicidilmetakrilata i etilenglikoldimetakrilata (EGDMA),skraćeno: PGME. Modifikacijom osnovnih uzoraka kopolimera u reakcijama saetilendiaminom (eda), dietilentriaminom (deta) i trietilentetraminom (teta),dobijeni su uzorci amino-funkcionalizovanih kopolimera: PGME-en, PGME-deta iPGME-teta.Određen je elementarni sastav osnovnih i amino-funkcionalizovanihuzoraka umreženih makroporoznih PGME mikroanalizom, a zatim suokarakterisani infracrvenom spektroskopijom sa Furijeovom transformacijom(FTIR). Osnovni parametri poroznosti sintetisanih kopolimera - specifičnazapremina pora, Vs, i prečnik pora koji odgovara polovini zapremine pora, DV/2,određeni su metodom živine porozimetrije i pomoću tih vrijednosti je izračunataspecifična površina pora, SHg.U eksperimentima sorpcije odabranih zagađujućih supstanci ispitivana jeefikasnost uklanjanja sintetičkih tekstilnih boja, teških metala i radionuklida izvodenih rastvora.Uzorak PGME-deta je izabran za ispitivanje sorpcije kisele boje Acid Orange10 (AO10) i reaktivne boje Reactive Black 5 (RB5). Ispitan je uticaj mase sorbenta ipH vrijednosti rastvora boje na efikasnost sorpcije obe boje, kao i uticaj režimamiješanja, da bi se odredili optimalni eksperimentalni uslovi. Zavisnost brzinesorpcije od koncentracije rastvora boje za AO10 je ispitivana u opsegu od 20-70 mgdm-3, a za RB5 u opsegu od 30-150 mg dm-3. Dobijeni kapaciteti sorpcije su biliosnova za proučavanje kinetičkih i difuzionih modela sorpcije odabranihsintetičkih boja, takođe i adsorpcionih izotermi.Da bi se ispitao mehanizam procesa sorpcije primjenjeni su modeli pseudoprvogi pseudo-drugog reda, model unutarčestične difuzije i Mek Kejev model. Zaanalizu sorpcione ravnoteže korišćeni su Langmirov i Frojndlihov model izoterme.Selektivnost kopolimernog sorbenta je ispitivana iz binarnih rastvora boja AO10 iBemacid Gelb, kao i AO10 i Bezaktiv Rot, a upoređena je efikasnost sorpcije bojeAO10 na aktivnom uglju i PGME-deta. Uticaj temperature rastvora boje nakapacitet sorpcije je ispitana na četiri različite temperature za tri različitekoncentracije RB5.Sorpcija šestovalentnog hroma je ispitivana pomoću PGME-deta izjednokomponentnih vodenih rastvora različitih koncentracija, binarnih rastvorajona hroma i bakra, kao i višekomponentne smješe jona hroma, bakra, kobalta ikadmijuma. Upoređena je brzina sorpcije Cr(VI), Cu(II), Co(II) i Cd(II) jona,izračunati kapaciteti sorpcije i dobijeni rezultati analizirani primenom modelapseudo-prvog i pseudo-drugog reda, kao i modela unutarčestične difuzije.Radi detaljnije analize uticaja pH vrijednosti na sorpciju metalnih jonapomoću PGME-deta u vodenom rastvoru izvedeni su eksperimenti sorpcije Cu(II) iCd(II) jona bakra pri pH=4 i sorpcije Pb(II) jona, pri pH=2, na PGME-deta. Određenisu kapaciteti sorpcije, a zatim analizorani modelom pseudo-prvog i pseudo-drugogreda, kao i modelom unutarčestične difuzije. Uzorci kopolimera sa vezanimmetalnim jonima su analizirani infracrvenom spektroskopijom (FTIR), snimljeniskenirajućom elektronskom mikroskopijom sa energetsko disperzivnomspektroskopijom x-zraka (SEM/EDX), a rendgenska fotoelektronskaspektroskopija (XPS) je urađena da bi se otkrile promjene elementarnog hemijskogsastava osnovnog kopolimera i prisustvo funkcionalnih grupa na površinimodifikovanog uzorka PGME-deta. Spektar visoke rezolucije (HRES) za C1s, N1s,Cd3d, Cu2p i Pb4f je snimljen da bi se ispitale interakcije između jona metala iamino grupa.Vodeni rastvori pertenetatnog jona, 99mTcO4-, su korišteni za uklanjanjeradionuklida pomoću dva amino-funkcionalizovana uzorka kopolimera, PGME-en iPGME-teta. Ispitivan je uticaj pH vrijednosti na kapacitet sorpcije izotopa 99mTc, aza analizu dobijenih rezultata su upotrebljeni modeli pseudo-prvog i pseudodrugogreda. The goal of this doctoral dissertation was to investigate the possibility ofpractical application of macroporous crosslinked amino-functionalized copolymersbased on glycidyl methacrylate (GMA) as a sorbent for the removal of variouspollutants from aqueous solutions.Two initial samples of copolymer glycidyl methacrylate and ethyleneglycol (EGDMA) - abbreviated: PGME, were synthesized by suspensioncopolymerization. By modification of the basic copolymer samples in reactionswith 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 PGMEand amino-functionalized samples was determined by miceoanalysis, and thesamples were further characterized by Fourier transform infrared spectroscopy(FTIR). The porosity parameters of copolymers - specific pore volume, Vs, and thepore diameter corresponding to half the pore volume, DV/2, were determined bymercury porosimetry and specific surface of pores, SHg, was calculated by usingthese values.The removing efficiency of selected pollutants from aqueous solutions, suchas synthetic textile dye, heavy metals and radionuclide, was investigated bysorption experiments.Sample PGME-deta was selected for testing the sorption of acidic dye AcidOrange 10 (AO10) and reactive dye Reactive Black 5 (RB5). The influence of themass of absorbent and pH value of the dye solution on the sorption efficiency ofboth dyes and the effect of mixing regimes was investigated in order to determineoptimal experimental conditions. The dependence of the sorption rate on theconcentration of the dye solution for AO10 is examined in the range of 20-70 mgdm-3 and for RB5 in the range of 30-150 mg dm-3. The obtained sorption capacitiesfor selected synthetic dyes were the basis for kinetic analysis with kinetics anddiffusion 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 sorptionmechanism investigation.Langmuir and Freundlich model isotherms were used forthe analysis of sorption equilibrium. Selectivity of copolymer sorbent is studiedfrom the binary solutions, AO10-Bemacid Gelb and AO10-Bezaktiv Rot. Thesorbent efficiency of active coal and PGME-deta for AO10 sorption were compared.The influence of dye solution temperature on the sorption capacity was examinedat four different temperatures for three different concentrations of RB5.The sorption of hexavalent chromium was studied using PGME-deta fromone-component aqueous solutions of different concentrations, binary solutionchromium 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 metalions sorption of the sorbent PGME-deta in an aqueous solution, the sorptionexperiments were performed for Cu(II) and Cd(II) ions at a pH=4 and the sorptionof Pb(II) ions at pH=2. The sorption capacities were calculated, and tested withPFO and PSO models, as well as the intraparticle diffusion model. Copolymersamples with bound metal ions were analyzed by Fourier transform infraredspectroscopy (FTIR), and scanning energy-dispersive X-ray spectroscopy(SEM/EDX). X-ray photoelectron spectroscopy XPS analysis was performed todetect changes in elemental chemical composition of the initial copolymers and thepresence of functional groups on the surface of modified samples PGME-deta. Thehigh resolution spectrum (HRES) for C1s, N1s, Cd3d, Cu2p and Pb4f was made tocharacterize the interaction between the metal ions and amino groups.Removal of radionuclides from aqueous solutions and the pH effect onthe sorption capacity of the isotope 99mTc was studied by sorption of pertechnetateions (99mTcO4-) onto two copolymer samples: PGME-en and PGME-teta. Theobtained results were analyzed by PFO and PFO models.