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