Analysis of phenol adsorption on raw and rnodified carpathian diatomite

Dwa naturalne adsorbenty diatomitowe (surowy i modyfikowane powierzchniowo) zostały użyte do usuwania związków fenolu z roztworów wodnych. Właściwości adsorpcyjne diatomitów zostały określone metodą statyczną i dynamiczną. Badania przeprowadzono na modelowym roztworze fenolu o stężeniu początkowym C0 = 20 mg/dm3 dla temp. 20°C. Przeprowadzona modyfikacja surowego diatomitu związkami manganu zwiększyła jego powierzchnię właściwą o 80% i zmieniła strukturę powierzchni. Dla obu testowanych diatomitów proces adsorpcji dobrze opisywały izotermy adsorpcji Freundlicha. Zdecydowanie lepszym adsorbentem (większą pojemnością adsorpcyjną) wykazał się diatomit modyfikowany D-Mn. W badaniach stwierdzono, że adsorpcja fenolu nieco lepiej zachodziła przy odczynie kwaśnym. Usuwanie fenolu w warunkach dynamicznych, w procesie filtracji na złożu D-Mn, z czasem kontaktu tk = 9 min, okazało się bardzo skuteczne. Pojemność adsorpcyjną w punkcie przebicia złoża wyniosła Pp = 12,6 mg/g. Diatomit D-Mn może być przydatny do oczyszczania wody lub ścieków zawierających fenol.Two natural diatomite adsorbents (raw and surface-modified diatomite) were used for removing phenol compounds from water solutions. The adsorptive properties of diatomite have been determined using static and dynamie methods. The tests were performed with a model solution of phenol at initial concentration of C0 = 20 mg/dm3, at the temperature of 20°C. A modification of raw diatomite with manganese increased its specific surface area by 80% and changed its surface srructure. For both tested diatomite grades the adsorption processes were described adequately by Freundlich adsorption isotherms. Modified diatomite, D-Mn, exhibited markedly better adsorbent properties (including higher adsorptive capacity). The tests showed that phenol adsorption proceeded slightly better in acid environment. Phenol removal in dynamie conditions, in a process of flltration on D-Mn bed, with contact time of tk = 9 min, appeared very effective. The adsorptive capacity at bed breakthrough point was PMn = 12.6 mg/g. The test conducted within the project showed that the D-Mn diatomite could be useful for conditioning of water or wastewater containing phenol

Natural and modified minerals in remediation of groundwaters

W artykule zsyntetyzowano wyniki badań dotyczących usuwania żelaza, manganu i azotu amonowego z wód podziemnych w procesie filtracji. Jako materiały filtracyjne stosowano minerały w formie naturalnej oraz zmodyfikowanej, takie jak: piasek kwarcowy, masa MZ-10, masa Defeman, modyfikowany klinoptylolit oraz przetworzony zeolit o nazwie Crystal-Right. Złoże z piasku kwarcowego usuwało żelazo łatwowytrącalne i stosowane było jako pierwszy stopień filtracji. Skutecznym procesem odmanganiania (drugi stopnień filtacji) okazała się filtracja przez masę uaktywnianą nadmanganianem potasu (VII) o nazwie MZ-10 oraz rudę manganową (złoże brausztynowe) o nazwie Defeman. Masy chemicznie aktywne zmniejszały również w pewnym stopniu zawartość azotu amonowego. Wysoka cena masy MZ-10 skłoniła autorów artykułu do poszukiwania jej zamiennika, którym mógłby być klinoptylolit. Porównując obydwa złoża można stwierdzić, że masa MZ-10 skuteczniej od klinoptylolitu usuwała z badanej wody podziemnej mangan oraz związki powodujące barwę i mętność. W odniesieniu do związków żelaza klinoptylolit i złoże MZ-10 pracowały porównywalnie. Porównując natomiast hydraulikę obu złóż można stwierdzić, że lepszym okazał się klinoptylolit. Na złożu MZ-10 szybciej wzrastały opory filtracyjne, co będzie skutkowało koniecznością częstszego płukania mechanicznego. Pomimo gorszych efektów uzyskiwanych z zastosowaniem modyfikowanego klinoptylolitu złoże to może być konkurencyjne w stosunku do masy MZ-10 z uwagi na jego niższą cenę. Należy liczyć się z lepszą pracą tego złoża w kolejnych cyklach filtracyjnych, po wytworzeniu się naturalnych powłok składających się z dwutlenku manganu i tlenków żelaza. Wysokim wymaganiom odnośnie usuwania związków żelaza i manganu oraz azotu amonowego sprostała przetworzona masa zeolitowa Crystal-Right 100. W I cyklu filtracyjnym złoże Crystal-Right 100 usuwało skutecznie żelazo, azot amonowy oraz do pewnego momentu mangan. W początkowej fazie pracy złoża nastąpiła znaczna obniżka twardości wody. Regeneracja zużytego złoża solanką przywróciła tylko w pewnym stopniu właściwości oczyszczające złoża (II cykl filtracyjny). Żelazo usuwane było skutecznie w całym cyklu, natomiast znacznie gorsze efekty uzyskiwano w zakresie usuwania manganu i azotu amonowego.The paper is a synthesis of results of research concerning removal of iron, manganese and ammonia nitrogen from groundwaters in filtration process. Minerals in both natural and modified forms, as: quartz sand, catalytic mineral masses, MZ-10 and Defeman, modified clinoptylolite and processed zeolite named Crystal-Right were applied as filtration materials. Quartz sand bed removed easily precipitable iron and it was applied as the first stage of filtration. Filtration through a bed mass, activated with potassium permanganate (VII) named MZ-10 and through manganese ore named Defeman (battery manganese bed), appeared to be effective process for removal of manganese (second stage of filtration). Active chemical masses reduced also the contents of ammonium nitrogen to some degree. High price of the MZ-10 mineral mass induced the authors of this paper to search for its substitute, with clinoptylolite as the likely candidate. From comparison study of both beds it can be concluded that the MZ-10 catalytic mineral masses is more effective than clinoptylolite in removing manganese and other coloring and turbidity-causing compounds from groundwaters. In respect to iron compounds, clinoptylolite and the MZ-10 bed showed comparable performance. However, in hydraulic terms, clinoptylolite exhibited better characteristics in comparison of both beds. Filtration resistance grew at much higher pace in MZ-10 bed, with a resulting need to apply mechanical rinsing operation more frequently. Despite inferior results obtained with modified clinoptylolite, the cheaper clinoptylolite bed may still be competitive to the MZ-10 catalytic mineral mass. One should expect better performance of the clinoptylolite bed in subsequent filtration cycles, i.e. once natural coats, consisting of manganese dioxide and iron oxides, have developed. Processed zeolite mass, Crystal-Right 100, met high requirements for removing iron and manganese compounds, as well as ammonium nitrogen. In its first filtration cycle, the bed of Crystal-Right 100, was effective in removing iron, ammonium nitrogen as well as, up to a certain moment, manganese as well. In the initial phase of bed operation water hardness became reduced considerably. Regeneration of spent bed with brine restored its purifying qualities only to a certain degree (2nd filtration cycle). Iron was effectively removed over the entire cycle, while the results of removing manganese and ammonium nitrogen were much poorer

Assessment of Usability of Bentonite Clays for Removing Phenol from Water Solutions

The paper presents the results of laboratory testing of the potential use of bentonite clay from Dynowskie Foothills for removing phenol from model water solutions. Both natural clays and those treated with sodium carbonate, hydrochloric and sulfuric acids were used. The paper shows the characteristics of phenols occurring in natural water. The sources of phenols, i.e. household and industrial wastewater as well as municipal landfills and damps are given. The aim of the experiments was to determine a quantitative formulation of the adsorption process, as well as to describe the effect of various factors on the process itself. An attempt was made to solve the tasks using model experimental setups. Model phenol solution, concentration of 20,00 mg/L, prepared using distilled water was applied as an adsorptive. The phenol concentration in model solutions was determined using the linear relationship between the concentration of this compound and the absorbency value at the wavelength of 254 nm. The absorbency value was read with a SHIMADZU UV – 1601 spectophotometer using quartz cuvets with an absorbing layer 10 mm thick. The results obtained in a successive series of experiments performed under static conditions were described using basic izoterm equations i.e. those of Freundlich, Langmuir and BET. Freundlich’s equations best described the process. The adsorption capacity of the active clays tested was calculated on the basis of the isotherms. Natural clay had an adsorptive capacity of 0,74 mg/g, clay modified with hydrochloric acid 2,41 mg/g, clay modified with sulfuric acid 1,83 mg/g and clay modified with sodium carbonate 0,50 mg/g. Dynamic conditions were realised by the column filtration method. The adsorption columns were made of organic glass 32 mm in diameter, the filling height was 750 mm, filtration rate – 12 m/h. Filtration was performed from the top downwards. Filtration lasted each time until the moment of bed exhaustion, i.e. such a point where the concentration in the discharge becomes equal to that of the initial solution. The sorption effectiveness under flow conditions for bentonite clays was 100%. On the basis of the results obtained, the breakthrough curves, the so-called iso-planes, were prepared and served in turn to determine the adsorption capacities under flow conditions. The adsorptive capacities were higher than those determined through static conditions and these were 15,9 mg/g, 19,9 mg/g, 18,8 mg/g and 15,2 mg/g for natural clay, clay modified with hydrochloric acid, clay modified with sulfuric acid and clay modified with sodium carbonate, respectively. The clay modified with sodium hydrochloric acid exhibited the highest values of adsorption capacities, as determined under both static and flow conditions. Modification of samples with hydrochloric and sulfuric acids appeared advantageous for both technological and economic reasons. The exit curves (iso-planes) were used to determine the mass penetration zone (the adsorption front height), as well as to calculate the rate at which the mass-exchange zone advanced. The adsorption front height for the carbons tested was 3–5 times lower than the adsorption bed height, thus confirming the high effectiveness of clays in phenol removal. Despite this considerable superiority of active carbon as sorbent, bentonite clays may be taken into account in designing process systems, especially as insulating materials in relation to active carbon. The array of water conditioning processes to be employed for phenol polluted water should in each case be preceded by detailed and thorough technological studies

Removal of ammonia nitrogen from groundwater on chalcedony deposits in two-stage biofiltration process

This paper presents an evaluation of the effectiveness of the removal of ammonia nitrogen from the water with oversize content of iron and manganese. The study was conducted using a two-stage biofiltration process on chalcedony beds. Biofilters operated in series, with counter-gravity flow at the first stage and the second stage gravity biofiltration. The chalcedony bed working at first stage was pre-activated with 0,3% KMnO4 in order to increase the efficiency of manganese removal. The test system was supplied with model solution made on the basis of a tap water with the addition of iron(II) 1g Fe/m3, manganese(II) 1 g Mn/m3, and ammonium 1,15-3,6 g N/m3 The results obtained during the study confirm that the biological processes of water treatment using a two-stage biofiltration through the chalcedony bed are effective in the removal of ammonia nitrogen from groundwater. Despite the diversification of mechanisms to remove these pollutants, the results indicate that the removal of ammonia nitrogen and manganese from water are competitive processes. The presence of manganese affects on the process of nitrification and ammonia nitrogen removal efficiency, and nitrification process may interfere with the effectiveness of manganese removal from water during formation of nitrification deposits. It was found that the presence of both iron and manganese affects the efficiency of the removal of ammonium and formation time of biofilm. Chemical activation biofilter of first stage had an impact on the efficiency of removal of ammonium and manganese ions, and the analysis of content of these pollutants shows that up to 10 day the chemical oxidation processes were dominated in working bed. It is difficult, however, explain the fact that in the second step of biofiltration manganese was removed with high efficiency from the outset of experiment, despite the lack of chemical activation. Previous studies have shown little effectiveness in removing manganese on the type chalcedony. A single-stage of biofiltration used in study was insufficient to carry out the nitrification process and obtain potable water for human consumption. After the first stage biofiltration water did not satisfy the requirements in terms of nitrite, and manganese. The increase in contact time through the use of second-stage of biofiltration allowed to obtain water that meets all the requirements for drinking water. Time for nitrifying chalcedony biofilter to reach full capacity was 64 days. The balance of nitrogen compounds and oxygen consumption shows the complexity of biofiltration. The real oxygen consumption was significantly lower than suggested by stoichiometric calculations and amounted to about 2 mg O2/dm3 per each mg of nitrogen removed, which can suggest that the removal of ammonia nitrogen on researched bed can occur not only in the process of nitrification. The Anammox process as well as the assimilation may have the contribute in the removal of ammonia nitrogen in the biofiltration process

Evalution of the adsorption process efficiency in removing humic substances from water

W artykule przedstawiono wyniki badań laboratoryjnych dotyczących możliwości wykorzystania węgli aktywnych produkcji polskiej (WD-ekstra, WG-12, WG-15, AG-5 i DTO) do usuwania substancji humusowych z wody. Celem przeprowadzonych badań było ilościowe sformułowanie procesu adsorpcji, oraz ustalenie wpływu różnych czynników na jego przebieg. Nakreślone w celu pracy zadania próbowano rozwiązać posługując się modelowymi układami doświadczalnymi. Jako adsorptyw stosowano roztwór modelowy zawierający substancje humusowe w ilości 20 mg/dm3. Procesy adsorpcji prowadzone w układzie porcjowym najlepiej opisywały izotermy Freundlicha. Na podstawie izoterm wyliczono zdolność adsorpcyjną testowanych węgli aktywnych. Warunki przepływowe realizowano metodą filtracji kolumnowej. Na podstawie uzyskanych wyników sporządzono krzywe przebicia–izoplany, które posłużyły do wyznaczenia pojemności adsorpcyjnych w warunkach przepływowych. Największe wartości pojemności sorpcyjnych wyznaczone zarówno w warunkach nieprzepływowych jak i przepływowych posiadały węgle WD – ekstra (7,71 mg/g) i DTO (7,40 mg/g). Krzywe wyjścia (izoplany) wykorzystano również do określenia strefy przenikania masy (wysokości frontu adsorpcji) oraz do obliczenia prędkości przesuwania się strefy wymiany masy.The paper presents the results of laboratory tests on possibility of utilizing active carbons produced in Poland (WD-ekstra, WG-12, WG-15, AG-5 and DTO) for removing humic substances from water. The objective of the tests was to arrive at a quantitative formulation of the adsorption process, as well as determine the effect of various factors on process course. An attempt was made to solve the tasks set in the study purpose using model experimental setups. A model solution with humic substances in the concentration of 20 mg/dm3 was employed. The processes of adsorption conducted in a batch mode were best described by Freundlich isotherms. The adsorption capacity of the tested active carbons was calculated on the basis of the isotherms. The flow conditions were created with columnar filtration method. On the basis of the obtained results, the breakthrough curves, so-called iso-planes, were prepared and served to determine the adsorption capacities in flow conditions. The WD-extra (7.71 mg/g) and DTO (7.40 mg/g) carbons exhibited the highest values of adsorption capacities, as determined in both non-flow and flow conditions. The exit curves (iso-planes) were also utilized to determine the mass penetration zone (the adsorption front height), as well as to calculate the rate of mass-exchange zone advance

Activated carbon usage for purification of water solutions with oil contaminants

Zaprezentowano rezultaty badań nad wykorzystaniem adsorpcyjnych właściwości wybranych pylistych węgli aktywnych do usuwania z wody zemulgowanego oleju maszynowego Mixol S metodą koagulacji. W badaniach zastosowano następujące reagenty: pylisty węgiel aktywny Organosorb 200-1 Wi (PWA 1). Organosorb 100-1 (PWA 2) oraz koagulanty podstawowe, tj.: chlorek żelaza(III) FeCl3 6H2O i siarczan(VI) glinu Al2(SO4)3 18H2O. Badania wykonywane były seriami w zależności od dawki pylistego węgla aktywnego (PWA) i rodzaju koagulantów podstawowych. Większą efektywnością w usuwaniu oleju Mixol z wody, przy użyciu obu koagulantów, wykazał się pylisty węgiel aktywny Organosorb 100-1 (PWA 2). Największe, 97% usunięcie oleju (Ck = 12 mg/dm3), przy stężeniu początkowym C0 = 360 mg/dm3, otrzymano dla 150 mg/dm3 Al2(SO4)3 i pylistego węgla aktywnego PWA 2 w dawce 0,2 g/dm3. W świetle przeprowadzonych badań koagulacja wspomagana procesem adsorpcji okazała się skuteczną metodą oczyszczania emulsji olejowych, a sole glinu lepszym koagulantem. Dużą korzyścią z zastosowania węgla aktywnego (czyli połączenia procesów koagulacji i adsorpcji) była lepsza jakość osadów pokoagulacyjnych. Osady uzyskiwane w wyniku prowadzonych testów z koagulantem podstawowym i węglami, w przeciwieństwie do osadów pochodzących tylko z samodzielnie stosowanych koagulantów, były o dużo większej gęstości i mniej uwodnione. Tworzyły szlam, łatwy do usunięcia i możliwy do regeneracji poprzez odwodnienie, wysuszenie i wyprażenie.The paper presents the results of research related to removal of oil emulsion (on base of 'Mixol S') from water solution in coagulation process. The selected powdery activated carbons were used as aid reagents by reason of adsorptive properties refer to organic compounds. The research was realized on model emulsion. Carried microscopic observation has showed that oil drops were smaller than 3.0 μm. It testified that objective emulsion could be described as fine-dispersion emulsion. The solutions have pH values in the range 6.5÷7.0. The following reagents were applied in the research tests: powdery activated carbon Organosorb 200-1 Wi (PWA 1), Organosorb 100-1 (PWA 2), as well as basic coagulants - i.e. iron(III) chloride FeCl3 · 6H2O and aluminum sulfate, Al2(SO4)3 · 18H2O. The tests were conducted in series, depending on the dose of powdery activated carbon and the type of basic coagulants. In case of PWA 1 (powder wood carbon) employment, removal of oil from water solution was considerable but not completely satisfactory. Final concentration of oil Mixol in water has amounted to C = 26 mg/dm3. It gets it at dose aluminum D = 90 mg/dm3 and 0.5 g/dm3 active carbon. When both coagulants were used the 'Organosorb 100-1' (PWA 2) powdery activated carbon exhibited higher effectiveness in removal of Mixol oil from water. The highest oil reduction, i.e. 97% (Ck = 12 mg/dm3), from its initial concentration of C0 = 360 mg/dm3, was obtained for 150 mg/dm3 of Al2(SO4)3 and for PWA 2 powdery activated carbon dosed at 0.2 g/dm3. Coagulation assisted by the adsorption process appeared to be a more effective method of water purification from oil emulsions, while aluminum salts were better coagulants. The big advantage of using powdery activated carbon (i.e. the combination of coagulation and adsorption processes), was a better quality of post-coagulation sediments. Unlike the sediments formed from coagulant used alone, the sediments obtained as a result of tests with basic coagulant and carbons had much higher density and contained less water. The sludge formed by the latter was easy to remove and could be regenerated by dewatering, drying and roasting

Using Ion Exchange Process in Removal of Selected Organic Pollution from Aqueous Solutions

Surfactant and phenol were removed using AMBERLITE IRA 900 Cl ion-exchange resin, which is a strong alkali. In the process, the tests were carried out under non-flow conditions, the effect of contact time and ionite dose on the surfactant and phenol exchange was determined. The tests under the through-flow conditions were realized in three consecutive cycles, preceded by regeneration and rinsing. The obtained results served for determination of ion-exchange capabilities of the studied ionite. The usable ion-exchange capabilities of the resin obtained after the second and third ionite operation cycle were lower by about 10% (surfactant) and 14.29-17.86% (phenol) than those after the first cycle. It shows that the process of sorption occurred simultaneously with the ion-exchange process

Application of Powdery Activated Carbons for Removal Ibuprofen from Water

The paper presents the results of studies on the use of adsorptive properties of selected powdered activated carbons (Norit SA Super and Carbopol MB5) for removal of ibuprofen from water. The tests were performed on non-flow conditions, series depending on the type and dose of powdered adsorbents. The research was carried out on a model solution of ibuprofen at initial concentration C0 = 20 mg/dm3, at 20 °C. Froundlich and Langmuir adsorption isotherms were used. Lagergrene kinetic models (PFO) and Ho (PSO) were used to describe adsorption kinetics. Both carbons exhibited a higher affinity for the adsorbent at pH above 7. Norit SA Super was a better adsorbent, for which, the highest adsorption capacity q = 0.448 g/g was achieved with dose D = 35 mg/dm3. The effectiveness of adsorption (decrease of ibuprofen in water) was 78%. The total removal of ibuprofen was obtained for a dose of carbon D = 200 mg/ dm3. With respect to Carbopol, the highest adsorption capacity (q = 0.353 g/g) was achieved at a dose of 30 mg/dm3, resulting in a 53% efficiency. Studies have shown that both tested powdered activated carbons have contributed to effective cleaning of aqueous solutions containing ibuprofen

Zastosowanie pylistych węgli aktywnych do usuwania materii organicznej z wody podziemnej

The article presents research results of the introduction of powdery activated carbon to the existing technological system of the groundwater treatment stations in a laboratory, pilot plant and technical scale. The aim of the research was to reduce the content of organic compounds found in the treated water, which create toxic organic chlorine compounds (THM) after disinfection with chlorine. Nine types of powdery active carbons were tested in laboratory scale. The top two were selected for further study. Pilot plant scale research was carried out for the filter model using CWZ-30 and Norit Sa Super carbon. Reduction of the organic matter in relation to the existing content in the treated water reached about 30%. Research in technical scale using CWZ-30 carbon showed a lesser efficiency with respect to laboratory and pilot-plant scale studies. The organic matter decreased by 15%. Since filtration is the last process before the individual disinfection, an alternative solution is proposed, i.e. the second stage of filtration with a granular activated carbon bed, operating in combined sorption and biodegradation processes. The results of tests carried out in pilot scale were fully satisfactory with the effectiveness of 70–100%.W artykule przedstawiono wyniki badań w skali laboratoryjnej, półtechnicznej i technicznej nad wprowadzeniem do istniejącego układu technologicznego stacji uzdatniania wody podziemnej, pylistego węgla aktywnego. Celem badań było obniżenie zawartości występujących w wodzie uzdatnionej związków organicznych, które po procesie dezynfekcji chlorem tworzą toksyczne związki chloroorganiczne (THM). W skali laboratoryjnej przebadano 9 rodzajów pylistych węgli aktywnych, z których dwa najlepsze wytypowano do dalszych badań. Badania w skali półtechnicznej realizowano na filtrze modelowym z zastosowaniem węgli: CWZ-30 i Norit Sa Super. Obniżenie materii organicznej w stosunku do jej dotychczasowej zawartości w wodzie uzdatnionej wynosiło ok.30%. Badania w skali technicznej z zastosowaniem węgla CWZ-30 wykazały nieco mniejszą skuteczność w odniesieniu do badań laboratoryjnych i badań w skali półtechnicznej. Obniżenie zawartości materii organicznej wyniosło ok. 15%. Ponieważ ostatnim procesem jednostkowym przed dezynfekcją jest filtracja, zaproponowano alternatywne rozwiązanie – drugi stopień filtracji ze złożem granulowanego węgla aktywnego, pracującego w połączonych procesach sorpcji i biodegradacji. Rezultaty badań zrealizowanych w skali półtechnicznej były w pełni zadowalające – skuteczność 70–100%