PROGRAM – THE NATIONAL PROGRAM FOR RESEARCH-DEVELOPMENT AND INNOVATION II – PARTNERSHIP IN THE PRIORITIES FIELD
PROJECT NO– 21-074 /September 2007
PROJECT TITLE – NEW TECHNOLOGY FOR URANIUM SEPARATION BY SOLVENT EXTRACTION IN ULTRASONIC ENVIRONMENT WITH BENEFICED IMPACT ON THE DECREASING CONTAMINATION OF THE INDUSTRIAL SURFACE-UEXUS
DURATION– 39 months (2007-2010)
PROJECT CATEGORY – COMPLEX project
REsearch field – D2-ENERGY
total budget – 1.172.390 LEI
FUNDS FROM OTHER SOURCES – 65.000 LEI
COORDiNATOR – Research and development National institute for metals and radioactive resources-ICPMRR Bucharest
Project manager – Dr. Eng. Eugenia Panturu
PARTNER 1 – ,,VASILE ALECSANDRI’’ University BACAU
Scientific Coordinator – prof. univ. dr. chim. Neculai Doru Miron
PARTNER 2 –,,AL.I.CUZA’’ University, Iasi
Scientific Coordinator -Prof.univ. dr .chim.Alexandra Raluca Iordan
PARTNER 3 -University POLYTECHNIC of bucharest – ECO-METALLURGICAL RESEARCH AND EXPERTISE CENTRE – CCEEM
Scientific Coordinator – S.L .dr .Eng .Mirela Sohaciu
PARTENER 4 – S.C. ECOPROIECT S.R.L. BUCHAREST-ECO
Scientific Coordinator –Physicist Cristina Niculescu
The project mAIN oBJECTIVE – is the decrease of the industrial surface contamination of Feldioara uranium ore processing plant by carrying out a new technology for uranium refining by liquid-liquid extraction in ultrasound environment.
The E.U. politics based on Directive 96/29 EURATOM – 2000 has the scope of decreasing, along time, of land surface contamination within the mining and milling areas used for radioactive ores. It is known that within the uranium ores processing, at the uranium refining stage by liquid-liquid solvent extraction, it results stable emulsions (known as third phase or crud), which incorporates both organic and aqueous phases having high uranium contents.
The degree of formation for these stable emulsions is determinate by the contribution of factors related to the impurities from uranium aqueous solutions which are subject for refining and also related to the operation manner. These stable emulsions, now technological wastes, are discharged to tailings ponds, contribution to the increase of contamination level, both of technological spaces where are manipulated and also of the storing ponds.
The general and specific objectives propose to be realized by the mentioned project are concordant with the objectives and priority’s of the programmed for technologies, both for environmental remediation and for avoiding poor environment quality due to industrial practices.
Using the ultrasonic chemistry within the uranium refining by liquid-liquid extractions process induces the scientific and technological complexity of the proposed research project.
The estimated benefits obtained following the project implementing are of ecological type, by reducing the impact of the refining on the environment factors, and also economic ones by increasing the processing yield due to lower technological losses.
The experience of the involved partners in solving the problems is a warranty of success chances for this project.
– 1/2007– Documentary study concerning acoustical cavity phenomena induce in liquids and stable emulsion formation decrease for uranium purification by liquid-liquid extraction on ultrasound field.
– documentation concerning causes of stable emulsions development for uranium purification by liquid-liquid extraction;
– study concerning acoustical cavity phenomena induce in liquids by ultrasound filed .
Abstract phase 1 – Done
For highlighting the activities, from the first phase of project, was approached next problem, namely:
a. causes of stable emulsion development for uranium purification by liquid-liquid extraction; to achieve this objective have been revealed these issues:
- factors favoring the formation of stable emulsion for uranium purification by liquid-liquid extraction are: impurities in the aqueous phase, impurities in the organic phase, working temperature and operating mode;
- types of solvents used at liquid-liquid extraction and their characterization – most used extractants are organophosphorus acids;
- Analysis methods of organic constituents – emulsion characterization – are most commonly used analysis methods for mono and dibutylphosphate with formation and breaking emulsion’s mechanisms.
b. study concerning acoustical cavity phenomena induce in liquids by ultrasound filed, by:
- theories statement of increase mass transfer in the field of ultrasound – cavity and acoustic current – production and effects;
- concepts statement of using ultrasound for reduction of stable emulsions formation – these processes occur with superior intensity that was necessary for liquid emulsion formation;
- Analysis and selection of implementation techniques of extractors with types of ultrasonic equipment used in industry and laboratories, for increase mass transfer and achieve the desired effect, by inducing cavity in the reaction medium.
– 2/2008 – Research concerning industrial areas of uranium processing plant contamination with radioactive elements and organic compounds due to stable emulsions
– study of dependent and independent variables for liquid-liquid extraction operation for uranium purification;
– chemical characterization of the uranium solution from liquid-liquid extraction purification plant;
– volume/weight determination of the stable emulsion;
– stable emulsion chemical analysis ;
– plant area contamination by the stable emulsion.
Abstract phase 2 – Done
For highlighting the activities, from the second phase of project, was approached next problem, namely:
a. study of dependent and independent variables for liquid-liquid extraction for uranium purification, to achieve this objective have been revealed these issues:
- chemical characterization of uranium solutions from L-L extraction;
- study of dependent and independent variables ( the extraction of HNO3 with TBP, uranium extraction with TBP/ kerosene, the effect of HNO3 concentration on uranium extraction process, watching the effect of mixing time, the effect of uranium and TBP concentration and temperature effect );
- volume/weight determination of the stable emulsion from L-L extraction;
- Stable emulsion characterization.
b. the determination of uranium contamination and pollution stable emulsion with organic substances of plant area, by:
- polluting and contaminating rate of plant area – characterization of factors witch influence the rate of pollution and contamination, namely: soil characteristics, type and extent of pollution, surface, further use area, remediation cost;
- contamination risk scenarios with radioactive substances and organic pollution of plant area – are the main stages of scenario and risk analysis;
- Monitoring and management of risk factors in pollution and contamination of plant area are the principles of validity and reliability of nuclear fuel facilities design, underlying monitoring and management of risk factors.
c. Research results dissemination – exchange of good practice – contains titles of articles presented by consortium members at scientific events home and abroad next to exchange of good practice for the observed increase in research.
– 3/2009 – Design and perform of the laboratory installation for uranium purification by liquid-liquid extraction.
– laboratory installation design;
– laboratory installation operation demonstration;
– results dissemination.
Abstract phase 3 – Done
For highlighting the activities, from the third phase of project, was approached next problem, namely:
a. development of experimental model of installation for uranium purification by liquid-liquid extraction, in laboratory conditions, by:
- establish basis for plant design laboratory;
- development documentation for installation execution laboratory;
- Building laboratory installation.
b. laboratory installation operation demonstration, by;
- nitrogenous uranium sample preparation solutions;
- organic solvents characterization;
- installation operation demonstration,
c. Research results dissemination – exchange of good practice- contains titles of articles presented by consortium members at scientific events home and abroad next to exchange of good practice for the observed increase in research.
– 4/2009 -Laboratory researches for uranium purification without ultrasound using.
– uranium solution physical-chemical characterization;
– stable emulsion determination for liquid-liquid extraction in plant parameters condition.
– results dissemination.
Abstract, phase 4 – Done
For highlighting the activities, from the third phase of project, was approached next problem, namely:
- uranium solution physical-chemical characterization – for purification of uranium by liquid-liquid extraction, in laboratory condition, uranium solutions were characterized with experimental measurements;
- stable emulsion volume determination for uranium purification –have been made experiments of liquid-liquid extraction for stable emulsion volume determination both in extraction funnels and the extractor module – has interoperated the experimentally obtained values;
- Research results dissemination – exchange of good practice- contains titles of articles presented by consortium members at scientific events home and abroad.
– 5/2010 – Conceptual model elaboration concerning uranium purification by liquid-liquid extraction under ultrasound field. Laboratory researches for uranium purification with ultrasound using.
– The optimum ultrasound field determination on liquid-liquid extraction by variable study;
– Determination of the stable emulsion volume for liquid-liquid extraction under ultrasound;
– Positive effect establishing for ultrasound using in liquid-liquid extraction on the radioactive contamination and stable emulsion pollution decreasing;
– Mathematical model statement and control for the studied process;
– Results dissemination.
Abstract step 5 – Done
To highlight the activities of the fifth stage of the project, the following issues were addressed, namely:
- – Determining the optimum field ultrasonic liquid-liquid extraction, through study variables – presents a study of behavior in the field of ultrasound systems, focusing on the theories underlying the cavity, but also the type of equipment and characteristics, which would ensure an optimal ultrasonic field intensification study. Alongside these are highlighted variables process and their way of measuring ultrasonic;
- – determining the amount of stable emulsions in the presence of liquid-liquid extraction, and ultrasonic extraction experiments were conducted to determine the volume of liquid-liquid emulsions stable in the ultrasound field in the separating funnel, using a generator Hielscher UP 400S, 24 kHz, 400W. Experiments have revealed that the amplitude of 100% and the distance sonotrod / 5mm sample, phase III is not totally eliminated, but its volumes are up to 42 times smaller than those formed in the absence of ultrasonic field and uranium solution acidity is not below 2.7 N, approaching the threshold of 2.8 N is required. Using higher power, but still in the system of low intensity, could lead to total elimination of phase III and / or reduction sonotrod-sample distance.
- – the development process for separating uranium solvent extraction in an ultrasonic field, contains the recommended optimal process parameters for the separation of uranium by solvent extraction in an ultrasonic field, but only in batch mode, achieved only in separating funnels, contacting a volume of AUI (aqueous continuous phase) with 3 volumes of organic fresh every time, in each of the six stages are: report the organic: aqueous 3: 1, no. speed: 6, for mixing: 5 min settling time: 10 min, the organic solvent is composed of 30% tributylphosphate (TBP) and 70% Kerosene, TBP was acidified with 1N nitric acid, containing depleted uranium in aqueous max . 0.5 gU/ L, containing uranium loaded organic solvent: min.100 gU/L, Temperature: 20 ° ± 5; ultrasonic frequency: 24 kHz ultrasonic time: 5 min.; distance sonotrod – sample: 5mm, amplitude: 100%.
- – verification of mathematical models describing the study– mathematical models are presented, which represents the response function (in this case the yield of extraction) of parameters obtained for the extraction process in the field of ultrasound, which verifies the experimental results which are valid in the study of the independent variables (amplitude ultrasonic concentration TBP / kerosene and aqueous phase acidity). In all three cases, we can draw the real values of optimum points of the optimal extraction process of uranium in the ultrasound field: the optimal content of uranium in aqueous phase is 310-315 g U / l, the optimum ratio of A: A is 1:3, the optimal free acidity of aqueous phase is 3.14 -3.19 N, TBP concentration in kerosene is 30%, the optimum number of extraction steps is a 6-speed 100% ultrasonic amplitude, the frequency of 24 kHz.
- – Dissemination of research results, exchange of good practice, includes titles of articles submitted by consortium members to national and international scientific meetings.
contribution of the KNOWLEDGE development in the studied field
Articles based on the project researches in the studied field.
a. National scientific meetings
- International conference of applied Sciences Chemistry and Engineering Chemistry CISA 2008, Bacau-Slanic Moldova, aprilie 2008, ’’ Aspects regardant la speciation de l’uranium dans les eaux de mine’’– E.Panturu, R. Radulescu, G.Jinescu, A. Filcenco-Olteanu, N.Groza, 2008, pag.28 , ISBN 978-973-1833-86-6 , Ed. Alma Mater, Bacau;
- international Conference –SIGPROT 2008-Editia a XI-a ,Politice Academy ,,Al.I.Cuza’’, mai 2008 , Bucuresti – ’’ the radioactive polluted soils’ decontamination using the ultrasound field’’– E.Panturu, R. Radulescu,I.C. Popescu, M.Flucus, 2008,pag.308 , ISBN 978-606-521-049-3, Ed. Printech ;
- XXX-th Romanian Chemistry Conference –2008 Calimanesti -Caciulata ’’Aspecte privind factorii favorizanti in formarea emulsiilor stabile la purificarea uraniului prin extractie cu solventi’’- E. Panturu, R. Radulescu, G. Jinescu, A. Filcenco-Olteanu, N. Groza, 2008, pag. 272,ISBN978-973-750-124-0 ;
- International conference of applied Sciences Chemistry and Engineering Chemistry CISA -CISA 2009, Bacau-Slanic Moldova, aprilie 2009, ’’ Uranium purification by liquid-liquid extraction using tributyl phosphate (TBP)’’– E. Panturu, A. Filcenco-Olteanu, N. Groza, C. Jinescu, 2009, pag. 209 , ISSN 2066-7817 , Ed. Alma Mater, Bacau;
- 11 –th Timisoara’s Academc Days , 2009,’’ Uranium Immobilization on Reactive Material Using RPB’’– E. Panturu, A. Filcenco-Olteanu, N. Groza, L. Ciobanu, 2009, pag. 118 , ISBN 978-973-52-0630-7, Ed. Academiei;
- Premier Colloque Francophone sur Les Materiaux, Les Procedes Et L’environnement iunie 2009 , Buşteni, România , ’’Préparation et caractérisation des ferrites de Ni et Mn obtenues par réaction de combustion’’ , A. R. Iordan, M. N. Palamaru, M. Airimioaei, p.72 ;
- International Conference on Applied Sciences, Slanic Moldova-Bacau, 2010, ’’Uranium Solvent Extraction using ultrasound’’, E., Panţuru, Antoneta Olteanu, N.Groza, R.I.Panturu, p.404-409,ISSN2066-7817;
- International Conference on chemistry and Chemical Engineering , Timisoara , mai 2010 ,’’Uranium purification increasing using ultrasounds’’, E., Panturu, R., I., Panturu, Ghe., Jinescu, A., Filcenco – Olteanu, N., Groza, , p. 402;
b. Intenational scientific meetings
- The 10th International Chemical and Biological Engineering Conference CHEMPOR 2008 Braga, Portugal, septembrie 2008, ’’Statistics model and optimization of uranium extraction in ultrasounds field in sulphuric acid medium’’- E. Panturu, R. Radulescu, A. Filcenco-Olteanu, 2008, pag.465, ISBN 978-972-97810-4-9, Ed.Ferreira and Mota;
- 1st International Exergy, Life Cycle Assessment, and Sustainability Workshop & Symposium, Grecia, iunie 2009,’’In situ decontamination of the underground water from uranium mining activities” – E. Panturu, A. Filcenco-Olteanu, N.Groza, V.Ciocan, pag.36;
- The XIII Balkan Mineral Processing Congress Bucharest , Romania, aprilie 2009, ’’Uranium solvent extraction from nitric solution’’, E. Panturu, A. Filcenco-Olteanu, N. Groza, C. Jinescu, R.I. Panturu, pag.632, ISBN 978-973-677-161-3, Ed.Focus -Petrosani;
- 4-th International Conference on the Enviromental Effects of Nanoparticles and Nanomaterials, Viena ,Austria, sept. 2009, ’’ Combustion synthesis and magnetical properties of nanocristalline co ferrites doped with manganese ’’,A.R. Iordan, M.N. Palamaru, T. Slătineanu, O.F. Călţun, I. Dumitru, L. Butiuc, pag.26;
- 4-th International Conference on the Enviromental Effects of Nanoparticles and Nanomaterials, Viena ,Austria, sept. 2009, ’’The optimization of synthesis conditions used for obtaining MnXNi1-xFe2O4 series ferrites. the study of electrical properties ’’,M. N. Palamaru, A. R. Iordan, M. Airimioaei, L. Leontie, C. Ciomaga, L. Mitoşeriu, A.V. Sandu, pag. 78;
- 42 nd IUPAC CONGRESS , Glasgow , UK, august 2009 , ’’Underground water decontamination by permeable reactive barrier”, E. Panturu, A. Filcenco-Olteanu, N. Groza, V. Ciocan, pag. P 407_012, Ed. RSC Advancing the Chemical Sciences;
- 16th Romanian International Conference on Chemistry and Chemical Engineering –RICCCE , Sinaia, sept. 2009 ,’’ uranium liquid-liquid extraction using tributylphosphat’’ , E. Panturu, N.Groza , A. Filcenco-Olteanu, C. Jinescu , R. I. Panturu, pag. SIV 194, ISBN 978-606-521-349-4, Ed. Printech Bucuresti;
- International Congress of Chemichal and Process Engineering ,CHISA 2010, Praga ,Cehia, 2010 , ’’the radioactive polluted soils’ decontamination using the ultrasound field’’, E. Panturu, G. Jinescu ,A. Filcenco-Olteanu ,R. Radulescu, r. I. Panturu, p.2000, ISBN 978-80-02-02250-3
c. Articles in international databases
- Journal of the European Ceramic Society, Volume 29, Issue 13, October 2009, Pages 2807-2813, In situ preparation of CoFe2O4–Pb(ZrTi)O3 multiferroic composites by gel-combustion technique, A.R. Iordan, M. Airimioaiei, M.N. Palamaru, C. Galassi, A.V. Sandu, C.E. Ciomaga, F. Prihor, L. Mitoseriu, A. Ianculescu.
- Review of Chemistry, 60,12, 2009,p.1318-1324, in situ decontamination of the underground water from uranium mining activities, E., Panţuru , Ghe., Jinescu,R., Panturu, N., Groza,A.,Filcenco–Olteanu,ISSN0034-7752
Best practice exchange
- Symposium “Partnership in priority areas – Monitoring elements of projects funded” may 2008, Sinaia, Romania, – organized by National Management Programs Center – CNMP;
- Du Littoral Cote D`Opale University, Dunkerque, France, may 2008, partner 2 – research stage on heavy metals separation technologies;
- Osnabruck University, Germany, – partner 1 – Roundtable and Training with title “Depollution of environmental – European priority” – June 2008;
- Superior National School of Chemical Engineering and Technology, Toulouse, France, June 2008 – partner 2 – information, knowledge and experience exchange;
- Du Littoral Cote D`Opale University, Dunkerque, France, October 2008 – visibility promotion and research excellence, next to exchange of good practice and – mutual knowledge of technical and scientific potential in order to achieve good conditions in the respective tasks of each partner in the contract – project coordinator;
- Roundtable and workshop organized by Bacau University – partner 1, Slanic Moldova, 18.06 – 22.06.2008 – technical discussions;
- Roundtable and workshop organized by Bacau University – partner 1, Slanic Moldova, 18.11 – 23.11.2008 – technical discussions;
- Organizing the International Conference of Applied Sciences, Chemistry and Chemical engineering Bacau – Slanic Moldova, 2007, 2008, 2009 and 2010;
- Poitiers University, France – Fundamental and Applied Sciences Faculty and Paris University IX, France, Solid physical-chemical laboratory, July 2009- partner 2 – information, knowledge and experience exchange;
- Summer school organized by Bacau University – partner 1, South Eforie, 20.08- 1.09.2008 – technical discussion.
- Round table organized in the International Conference on Applied Sciences, Chemistry and Chemical Engineering, CISA 2010 Bacau-Slanic Moldova, in April 2010 with the theme,’ New technologies beneficial impact on the reduction of uranium contamination in the surrounding area”