RESEARCH ON USE OF REACTION barriers Wastewater treatment processing plants results Uranium ores – URTECH

Schedule: National Plan for R & D and innovation II Partnerships in priority areas

Research direction: D3-Environment

Competition: June 2007

No project: 31 093

Duration: sepembrie 2007 – Sept. 2010

Title: RESEARCH ON USE OF REACTION barriers Wastewater treatment processing plants results Uranium ores – URTECH

Contracting Authority: National Centre for Project Management – CNMP

Project Coordinator:

National Institute for Metals Research and Development ICPMRR Radioactive Resources, Bucharest, Romania

Project Director: Phd eng. Antoneta Filcenco – Olteanu, e-mail: afilcenco@icpmrr.ro

Partner 1: UBC University-Bacau, Romania

Project Manager: Dr. Denisa Ileana Nistor

Partner 2: AI Cuza University Iasi UAIC , Romania

Project Manager: Prof. Dr. Mircea Palamaru

Partner 3: ECO SC ECOPROIECT Ltd., Romania

Project Manager: fiz. Cristina Niculescu

The aim of this complex project is the development, in partnership, of modern environmental technologies for treatment, the source, sewage from uranium alkaline processing plant is required by the rules issued by CNCAN to avoid contamination of water surface or groundwater. In accordance with EU policy, and consequently of our country, in terms of sustainable use of water (Water Framework Directive, 2000/60/EC), the major objective is to reduce time to load contaminated waste waters. The proposed technological process of use of reactive barriers is a eco-technology because it is a passive method of treating polluted water (without supply of energy and building surface), and pollutants are transformed in a form acceptable to the environment.

The complex character refers to the implementation of a modern method of remediation of waste water with complex composition using nanostructure materials specific pollutant retention components. Project involves achieving the objectives pursued in partnership structures of nanomaterials, characterization and determination of performance these data, determining static and kinetics of retention of pollutants by the process selected, determining the composition of the reactive barrier, achieving an experimental model of column percolation experiments in natural conditions of process, technology development and process parameters and Demonstration of functionality and usability of the process. EU policy (based on EU Directive 96/29 Euratom, 2000) is aimed at reducing surface water affected by pollutants and radioactive especially those affected in order their reintroduction into the circuit as waters clean.

General and specific objectives of proposed project are consistent with program objectives and priorities for development in partnership of innovative environmental technologies for restoration of natural environment. Using nanomaterials prepared within our team to accelerate the decontamination process physicochemical water induces scientific and technical complexity of the proposed project, by applying theories and transfer mechanisms in solid-liquid heterogeneous systems by integrating them into the reactive barrier innovative technique of treating the source of pollution and evaluate the operating parameters of withholding evidence in a form of chemical pollutants friendly environment.

Benefits of what is expected to achieve after implementing the project are: reducing the impact of conservation officers or nuclear installations on the environment, bringing wastewater quality parameters that allow their classification in grade water clean while extremely low.

Specific objectives:

Phase I – Done

Documentation and listing of technology solutions for use in designing nanostructure materials reactive barriers for waste water treatment, physico-chemical characterization and monitoring of wastewater composition, 12/15/2007

Documentation and statement solutions for synthesis, characterization and the possibilities of using nanostructure materials comprised Reactive Barriers.
Physical-chemical characterization and monitoring of wastewater composition.
Analysis and selection techniques of the column leaching

Stage II: Done

Identification of optimal reactive barrier components depending on the type of pollutants present, synthesis, characterization and test-tion capacities of nanostructure materials remediation, 11/30/2008

Synthesis in laboratory phase Characterization of nanostructure materials;
Laboratory testing capacity for synthesized nanostructure materials remediation.
Develop design documentation columns percolation of model laboratory design
Research results dissemination, exchange of good practice.

Phase abstract

For decontamination by reductive precipitation research has focused on the synthesis and use of nanocompounds of zero valent iron, and for adsorption remediation has studied clay nanostructured materials.

From the group of materials based on nanostructured iron were synthesized and characterized:

Nanostructured zero-valent iron reduction method of soluble salts leading to particles with a size of 211 nm according to characterization performed by Zetasizer Nano _ ZS ZEN 3600.
Nanostructured iron deposited on solid support such as: AG 20G Purolite type active charcoal, C 160 Purolite resin versus ARSEN -X ^np Purolite; the electronic transmission microscopy characterization method indicate that nanostructure iron submission on the two types of solid support.

From group of clay materials the montmorillonite modified clays were used by Romanian origin (Valea Chioarului). Modified clays were obtained with Al polyhydroxide, Fe (II) polyhydroxide and Cu polyhydroxide.

Characterization was made with electron microscopy, x-ray diffraction measurement of specific surface (BET method). Emphasizing surface properties achieved with the completed installation of scheduled thermo-desorption.

Tests conducted to establish the capacity of remediation materials led to these summarized conclusions:

a) Remediation ability nanostructure materials iron based is directly proportional to the amount of iron present in nanostructure reactive material and adsorption properties of support:

– Distribution coefficients for uranium values are related to nano iron content of reactive material and of adsobtive property of reagent material. Most efficient is Purolite ARSEN – X resin, the distribution coefficient indicates that aggregation of quantity of nano iron deposition on the resin with adsorptive proprieties for uranium of used macro porous resin.

In case of molybdenum, the only reactive materials witch contains nano iron, on the tested which can eliminate molybdenum compound containing activated charcoal. Fact that activated charcoal adsorbed molybdate from solution, immobilized it.

The degradation of nitrate ion is direct proportional with nano iron quantity from reagent material

Test on the uranium rate with nano iron from waste waters indicates that resin ARSEN –X has the best kinetics, after only 24 hours the uranium content decreases at 0.096 gU/L.

Test using Purolite Arsen X resin column followed the optimal flow determination, study the influence of initial concentration on the loading of resin and the loading kinetics. Concluded that the optimum flow rate is 3 BEV/h, resin load is obviously influenced by the uranium concentration reaching a load of 32,23 g/l for resin alimentation solution of 175 mg/l. The kinetics study of loading with uranium shows that after 4800 BEv (48 l of solution with uranium content of 1.16mg/l) the resin is loaded with 5.32 gU/l resin, the uranium content in effluent is under detection limit, then increase till alimentation concentration value.

Remediation capacity of clay-based materials was studied using kinetics tests in solutions containing uranyl cations, following the influence of temperature on the time evolution of the degree of cation ion exchange UO ²⁺ variant agitated batch detector – dynamic regime. There was a relatively large capacity of pollutants retaining on clay copper cation, depending on temperature. For a limited contact time: clay pollutant solution, modified clay with copper poly-hydroxyl cations has a high cation retainer capacity, which proves that the modified clay, greatly increases porosity, ion exchange and accessibility of surface pollutants cations at clay’s surface. By increasing the rate of diffusion and retention of uranyl cations in the clay structure accelerates and streamlines the process of remediation radioactive waste water. Remediation process based modified montmorillonite clays with copper poly-hydroxy cations is done with an efficiency of 99.9% which removes the risk of radioactive cations remain in the water.

To develop design documentation leaching columns and design laboratory experimental model was prepared specifications and technical documentation developed by the battery performance of columns.

Dissemination and exchange of good practice realized through the organization of a international conference, presentation of scientifically papers at interns and international manifestation, roundtable and technical meetings.

Stage III: Done

Reactive barrier design and laboratory testing by the column-leaching 11/30/2009

The development of experimental model of leaching column

Results dissemination, exchange of good practice

Phase abstract

In this phase the research focalized in first place on the development of experimental model. For reductive precipitation remediation research focalized on the synthesis and use of zero valent iron nanocompounds, and for adsorption remediation had studied nanostructure clay’s materials.

Reactive barrier design was based on research conducted in earlier stages and thus were selected as the reactive barrier material constituting these:

– Purolite ARSEN resin – tests on the removal speed of uranium waste by nanoiron indicate that resin has the best kinetics, after only 24 hours de uranium content decreases from 1.16 g/l to 0.096 g/l.

– Modified clay by copper cation – remediation capacity of clay-based materials was studied consequences of using tests in solutions containing uranyl cation, following the influence of temperature on the time evolution of the degree of cation ion exchange UO ²⁺ variant agitated batch detector _ dynamic regime. Modified montmorillonite clays with poly hydroxyl copper cations remediation process is done with an efficiency of 99.9% which removes the risk of radioactive cations remain in the water.

Based on technical documentation had realized the experimental model with these characteristics:

overall dimensions

columns dimensions – diameter

– length

– caps – sockets provided with thin web of stainless material for lizards loss reagent material

mounting position – vertical

glass valves – with two ways (for access), three ways (for sampling)

maximal pressure in system – 2 bar

flow – adjustable 0.1….2.5l/min

adjustable flow – fine and flow value display

technical characteristics of chosen dosing pomp – type – diaphragm pomp

motor type – motor DC with permanent magnet

alimentation 24 Vcc

maximum flow 2,5 l/min

connection tube

net weight 420 g

function : horizontal position

Regarding wastewater composition characterization from uranium ore processing plant are the main sources of pollutants that reach solutions pond plant, and characteristics samples taken during the project development. Composition of pond water monitoring found that the overtaking NTPA is made to the following parameters ph, total suspension materials, carbon content of organic nature, azotes compounds (ammonia azotes, total azotes, nitrates, nitrites), and substances extractable in ether, petroleum, uranium, molybdenum and chlorides.

Stage IV: Done

Technology development and process parameters, functionality Demonstration boundary to natural conditions at laboratory-15.09.10

test of leaching

mathematical interpretation of the results

Phase abstract

In this project are presented research for materials remediation and capacity of tests, for wastewater treatment from ore processing plant.

The mode of realization of this objective:

used materials permeable barrier characterization :

Purolite Arsen X resin

Active charcoal (carbon) ac – 20 g Purolite on witch has loaded zero valent iron

Modified clay mixed with zeolite from Slaic Prahova area.

Leaching achievement tests using plant experiments in this experimental installation made in this scope in anterior phase of the project. Three glass columns have been loaded; first with Purolite Arsen resin, second with AC – 20 G Purolite carbon doped with iron nanoparticle, and third with a mixture of zeolite from Slanic – Prahova with modified montmorillonic clay. Each column had diameter of 0.06 m (d= 0.03m) and length of 0.50 m. leaching tests were realized trough type 2“factorial programming in witch the naturals factors were water flow trough the exchange layer, total volume of reagent material and wastewater ph, and process response were – breakthrough time, time of saturation and efficiency of ionic exchange process.

Mathematical processing of results obtained by developing statistical models that express the influence of three important factors of process (liquid flow rate trough layer, height of exchange layer- through volume – ph ) the volume of water processed to breakthrough, that up to saturation, and the effectiveness of using resin. Each of contaminants considered (uranium, molybdenum and nitrates) have obtained specific volume of decontaminated water to piercing, that up to saturation of reactive. These values, together with the efficiency of use of reactive, depending on factors were correlated with process `s factors.

Adjust these relationships so that they respond to other concentrations than those used in experiments and even to another composition, makes possible their use process sizing, although technology assessment

Stage V – done

Technology development and process parameters, demonstrate the functionality of the barrier under natural conditions at laboratory

Technology development

Research results dissemination

Based on research will develop a conceptual model of cross treatment technologies, source, wastewater from a processing plant alkaline uranium ore, to avoid contamination of surface water or groundwater.

Demonstration of functionality of the proposed solution, develop technology
Final characterization of leaching column developed under
Disseminating research results

Developed innovative ecotehnology aims wastewater decontamination from a plant for processing uranium ore and waste water quality classification will be discharge into natural water resources in NTPA-001/2002 prescriptions.

The technology is based on the use of reactive barriers which have as components reactive nanostructured materials specific of pollutants present in treated water.

Research conducted to establish the materials used for the selection of barriers allowed Purolite Arsen^Xnpresin, which will retain uranium, Purolite type AC 20G coal doped with zerovalent iron, which retains molybdenum and copper modified montmorillonitic clay which will retain both uranium and nitrates present in subjected to water decontamination.

Copper modified montmorillonitic fine-grained clay (<0.5mm) that disrupt the flow through the column in the sense that it slows down significantly, required mixing it with other natural material properties, namely a zeolite adsorption Slanic Prahova area.

To achieve that goal in this stage were established optimal technological parameters of process, and technological flow diagrams were developed on operations equipment, has developed a manual of technology presentation.

Proposed ecotehnology for water treatment form a plant prevented from processing uranium ore using reactive barriers with reactive components as nanostructured materials will find widespread application because of the advantages they present.

The „passive” character of process by avoiding contamination of additional operating costs due to simple technical solutions, the environmental efficiency of waste water containing heavy and radioactive metals are just some of benefits of ecotehnologies.

Results disemination :

Participation in national and international

Article TITLE / VOLUME / Scientific communications	Authors	*PROCEEDING )/ VOLUME /PAG/ ISSN/ ISBN/ EDITURE CONFFERENCE**
Depollution of uranyl polluted waters using pillaring clays	Nistor I.D., Miron N.D	Journal of Thermal Analysis and Calorimetry vol.89, nr.3, 2008, p.977-981; ISSN 1388-6150
Metal removal through synergic coagulation –flocculation using an optimized chitosan– montmorillonite system	Assaad E., Azzouz A., Nistor D., Ursu A.V., Sajin T., Miron D.N., Monette F., Niquette P., Hausler R.	Applied Clay Science Volume 37, Issues 3-4, 2008, p. 258-274; ISSN: 0169-1317
Thermogravimetric analysis of layered double hydroxides with chloramphenicol and salicylate in the interlayer space	Mihaela Frunza, Gabriela Lisa, M. I. Popa, N. D. Miron, Denisa Ileana Nistor	Journal of Thermal Analysis and Calorimetry Vol. 93, nr. 2, 2008, p. 373–379 ISSN 1388-6150
Characterization and utilization of commercial clay for ammonia adsorption. Influence of operating parameters on gas retaining	Ursu A.V., Gros F., Nistor I.D., Djelveh G.	Revista de Chimie, vol. 59, nr. 10, 2008 p. 1067-1072, ISSN: 0034-7752
Studiul imobilizarii uraniului din ape poluate radioactiv, de catre materiale reactive utilizabile in bariere permeabile reactive	R. Radulescu, E. Panturu,A. Filcenco-Olteanu, M.Flucus	XXX-th Romanian Chemistry Conference 8-10oct.2008, p.273 ISBN 978-973-750-124-0
Studiul unor proprietati ale materialelor neconventionale argiloase utilizate in intensificarea proceselor de depoluare a mediului	D. I. Nistor, N. D. Miron, A. V. Ursu, A. V. Arus , A. M.Mares, I.Siminiceanu, Abdelkrim Azzouz	XXX-th Romanian Chemistry Conference 8-10oct.2008, p.273 ISBN 978-973-750-124-0
Synthesis and characterization of organic phase gold nanoparticles obtained through chloroaurate ions reduction with sodium citrate	A. Filcenco-Olteanu , R. Radulescu, E. Panturu	10^thInternational Chemical and Biological Engineering Conference, 2-7 sept. 2008, Braga , Portugal,p.465 ISBN978-972-97810-4-9
Aspects regardant la speciation de l’uranium dans les eaux de mine	E.Panturu, R. Radulescu , Gh. Jinescu, A. Filcenco-Olteanu. L. Ciobanu, N. Groza , Gh. Filip, M. Flucus, L. Grigoras	Int.Conf. of Applied Sciences, Chemistry and Engineering Chemistry , CISA 2008,Bacau Slanic Moldova, 4-6 Apr. 2008 p.28-35 ISBN 978-973-1833-86-6
’’ ZERO-VALENT IRON USED FOR RADIOACTIVE WASTE WATER TREATMENT’’-	N.Groza, R. Radulescu, E.Panturu, A. Filcenco-Olteanu,	A 11 editie a Zilelor Academice Timisene , Mai 2009, pag.115 ,ISBN 978-973-52-0630-7, Ed. Academiei;
„PRÉPARATION ET CARACTÉRISATION DES FERRITES DE NI ET MN OBTENUES PAR RÉACTION DE COMBUSTION”, ,	Alexandra Raluca Iordan, M. N. Palamaru, M. Airimioaei,	Premier Colloque Francophone sur Les Materiaux, Les Procedes Et L’environnement 31.05-06.06.2009, Buşteni, România
RADIOACTIVE WASTE WATER DECONTAMINATION USING ZERO-VALENT IRON –	N.Groza, E. Panturu, A. Filcenco-Olteanu,	1st International Exergy, Life Cycle Assessment, and Sustainability Workshop & Symposium, Grecia, iunie 2009,pag.37;
„ECOLOGICAL SOLUTIONS OF CONTAMINATED ENVIRONMENT REMEDIATION FROM URANIUM MINING ACTIVITIES IN ROMANIA” ,	N.,Groza, P.D.Georgescu, E.Panturu, A. Filcenco-Olteanu	The XIII Balkan Mineral Processing Congress Bucharest , Romania 2009, Vol II pag.899, ISBN 978-973-677-161-3, Ed.Focus -Petrosani;
„uranium waste water decontamination using zero-valent iron”,	N.Groza, E. Panturu, A. Filcenco-Olteanu ,	42nd IUPAC CONGRESS , Glasgow , UK, august 2009 pag.P407_011, Ed.RSC Advancing the Chemical Sciences;,
4-th International „SYNTHESIS AND CHARACTERIZATION OF DOUBLE PEROVSKITE OXIDES IN Sr₂Ni_xCo_1-xWO₆ SERIES”,	Mircea Nicolae PALAMARU, Alexandra Raluca IORDAN, Karin POPA, Maria ALEXANDROAEI,	Conference on the Enviromental Effects of Nanoparticles and Nanomaterials Viena 6-9 sept 2009;
„Pasive treatment for environmental bioremediation from uranium mining activities in Romania” la al „ 16th Romanian International Conference on Chemistry and Chemical Engineering – RICCCE” Sept. 2009,	N. Groza, A. Manescu, E. Panturu, A. Filcenco- 0lteanu , R.I.Panturu	16th Romanian International Conference on Chemistry and Chemical Engineering – RICCCE” Sept. 2009, pag. SIV 202, Ed. Printech Bucuresti, ISBN 978-606-521-349-4.
Uranium wastewater treatment using wetland system	N. Groza, Al. Manescu, E. Panturu, A. Filcenco – Olteanu, R.I Panturu, C. Jinescu,	Revista de Chimie, Vol. 61, nr.7, iulie 2010, p. 680-684, ISSN 0034-7752, cotata ISI,
Comparative study on nanomaterials characteristics obtained from raw montmorillonite clay and purified montmorillonite clay	N. Platon, I. Siminiceanu, I.D.Nistor, N.D.Miron	The Annals Of The ,,Dunarea De Jos” University of Galati Fascicle II- Mathematics, Physics, Chemistry, Informatics Year III (XXXII), 2010, p. 421 – 425, ISSN – 2066 – 7124. Alte baze de date internationale
Synthesis of zerovalent iron used for the radioactive contaminated water treatment”	A. Filcenco-Olteanu, E. Panţuru, R.I. Panturu, R. Radulescu, Ghe. Jinescu	Buletin Stiintific Serie B: Chimie si Stiinta Materialelor, ISSN 1454-2331, Alte baze de date internationale – acceptat spre publicare, 2010
Synthesis and characterisation of nanocristalline Zn ferrites substitued with Ni	T.Slătineanu, A.R.Iordan, M.N.Palamaru, O.F.Călţun, V. Gafton, L. Leontie,	Materials Research Bulletin, ISSN: 0025-5408, cotata ISI, acceptat spre publicare 2010,
Preparation and characterization of new products obtained by pillaring process,	Platon N., Siminiceanu I., Nistor I.D.,.Miron N.D.,	Revista de Chimie , ISSN 0034-7752, cotata ISI acceptat spre publicare 2010
ecological solutions of contaminated environment remediation from uranium mining activities in Romania	E. Panturu, A. Filcenco-Olteanu, N. Groza	Conferinta Internationala de Stiinte Aplicate, Chimie si Inginerie Chimica-CISA 2010, Bacau-Slanic Moldova, 8 – 11 aprilie 2010, ISSN 2066-7817 , Ed. Alma Mater, Bacau;
Utilizarea barierelor reactive la tratarea apelor reziduale rezultate la uzinele de procesare a minereurilor uranifere	A. Filcenco-Olteanu,	Masa rotunda in cadrul Conferintei Internationale de Stiinte Aplicate, Chimie si Inginerie Chimica-CISA 2010, Bacau-Slanic Moldova, 8 -11 aprilie 2010.
Uranium immobilization on reactive material using RPB	A. Filcenco-Olteanu , E. Panturu, R. Radulescu	7th European Congress of Chemical and Process Engineering Praga, CHISA, 28 aug.-2 sept ,2010 – p. 2010, ISBN 978-80-02-02250-3
Radioactive waste water decontamination using zerovalent iron	A. Filcenco-Olteanu , E. Panturu, R.I. Panturu, Gh. Jinescu, N. Groza ,	11th international UFZ-Deltares/TNO Conference on Management of Soil, Groundeater & Sediments, 22-24.sept 2010, Proceeding, Salzburg Austria, ISBN 978-3-00-032099-6
The influence of the combustion agent on zinc ferrite properties	T. Slătineanu, A. R. Iordan, M. N. Palamaru, O. F.Călţun, L. Leontie, N. Apostolescu,	Conferinta Internationala a Societatilor de Chimie din Tarile S-E Europene – ICOSECS 7 – 15-17 septembrie 2010, Bucurest
The synthesis, characterization and properties study of zinc ferrite substitued with magnesium	Tamara Slătineanu , Alexandra R. Iordan, Mircea N. Palamaru, Ovidiu F.Călţun, Liviu Leontie,	Conferinta Nationala de Fizica, Iasi, 23-25 septembrie 2010.