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GADOLINIO

TIERRAS RARAS

GADOLINIO TIERRAS RARAS

VISION DE LAS APLICACIONES DE LAS TIERRAS RARAS

HISTORIA DEL GADOLINIO


Descubridor: Jean de Marignac. Lugar de descubrimiento: Suiza. Ao de descubrimiento: 1880. Origen del nombre: El nombre proviene del mineral del que se obtiene: la "gadolinita", nombrado as en honor del qumico finlands Johan Gadolin. Obtencin: El gadolinio fue observado espectroscpicamente por Marignac en 1880. El elemento se ha obtenido puro hace poco tiempo.

PROPIEDADES
ASPECTO PLATEADO. EN CONTACTO CON EL AIRE SE FORMA UN OXIDO COLOR MATE. PUNTO FUSION MUY ELEVADO 3800C ES MUY REACTIVO ARDE FACILMENTE EN EL AIRE ES 10 VECES MAS MAGNETIZABLE QUE EL HIERRO SE LE CLASIFICA COMO TIERRA RARA MEDIA NUMERO ATOMICO 64 DENTRO DE LOS LANTANIDOS ESTADO DE IONIZACION TRIVALENTE RADIO IONICO 1.193 AMSTRONG

APLICACIONES
SE UTILIZA PARA HACER ALEACIONES ESPECIALES PARA HACER IMANES PARA FABRICAR MATERIALES SUPERCONDUCTORES ES EL MEJOR REFRIGERANTE MAGNETICO PARA IMANES SUPERCONDUCTORES SE UTILIZA EN LOS VISORES DE RESONANCIA MAGNETICA FABRICACION DE FILTROS DE MICROONDAS PARA TELECOMUNICACIONES. LOS COMPUESTOS DE GADOLINIO SE EMPLEAN EN LOS TUBOS DE TELEVISIN A COLOR. SE APLICA PARA LA FABRICACIN DE CDS. DISOLUCIONES DE GADOLINIO SE EMPLEAN EN DIAGNSTICO DE ENFERMEDADES. COMO CONTRASTE INTRAVENOSO EN RESONANCIA MAGNTICA.

MINERALES CON GADOLINIO

Xenotita (xenotime)

Bastnacita

Monacita

ALTERNATIVA A LOS MINERALES RICOS EN TIERRAS RARAS


Las tierras raras se encuentran en asociacin con las rocas de fosfatos . Se las considera un subproducto en la fabricacin por la via humeda de cido fosforico y en la fabricacin de fertilizantes por la via nitrofosforica.

Mtodos de separacin rentable


La separacin , es dificil se emplean metodos especiales ,con compuestos organicos y con quelantes.

Formacin de compuestos de coordinacin sin carga Procesos de intercambio inico Procesos de solvatacin con asociacin inica

SOLVENTES DE EXTRACCION
Los solventes para la extraccin a partir de fosfatos ,pueden ser cidos grasos carboxlicos y tambien orgnicos del fosforo. Las tierras raras pesadas se extraen a pH ms bajo , que las tierras ligeras .

SOLVENTES DE EXTRACCION (2)


Los solventes extractantes ms usados son el bis(2-etilexil)hidrogen fosfato conocido como D2EHPA,HDEHP,DEHPA,EHPA Tambien se hace con cidos carboxlicos ,del tipo terciario, como el verstico ,el neodecanoico.Tambien se utilizan cidos naftenicos.

EL SOLVENTE ADECUADO

HDEHP P(O)OH [CH (CH ) CH(C H )CH O]


3 2 3 2 5 2 2

Bis(2-ethylhexyl) phosphate

OTRO SOLVENTE Acido Verstico

ESTRUCTURA DE LA ACCCION DEL

HDEHP

DESCRIPCION DEL TRATAMIENTO


El proceso se inicia en una fbrica de extraccin de cido fosforico Primero se hace una molienda y seleccin por gravedad para tener una fraccin favorable para el tratamiento posterior . A continuacin se deshace el residuo con hidrxido sdico. El residuo insoluble se filtra en continuo.

PASOS DEL PROCESO DE EXTRACCION


Disolvemos con cido ntrico 1,5 M.(o sulfurico)

Haremos una extraccion en contracorriente de 10 pasos, como disolvente de extraccin el (C8H17O)2 PO2H + Shellsol AB
a pH cerca de 1 se ( separan+arrastran) los diferentes iones de tierras raras ,elejimos la fraccin del 57 al 63 Esta fraccin que contiene ms Gd , se hace precipitar con cido oxalico . El precipitado se filtra y despues se hace un calentamiento a 450 para obtener los oxidos .Los metales obtinenen por calcinacin reductora a 1000C. El Gadolinio metal se separara magneticamente aprovechando que es extremadamente paramagnetico.

DIAGRAMA DE BLOQUES DE EXTRACCION DE GADOLINIO DE FOSFATOS DE TIERRAS RARAS DE LA MINA NOLAN AUSTRALIA

Ca5(PO4)3(F,Cl,OH)

residuos procedentes fabrica Ac.fosforico


15% DISOLUCION HDEHP SHELLSOL AB

MOLTURACION MINERAL

LAVADO SEPARACION POR GRAVEDAD

EXTRACCION LIQUIDA 10 ETAPAS ,CONTRA CORRIENTE

TRATAMIENTO CON HNO3

FILTRACIN

TRATAMIENTO CON Na(OH) 3horas

PRODUCCION FERTILIZANTES FRACCION LIQUIDA +H2C2O4


ACIDO OXALICO

FERENTES FRACCIONES TR LIVIANAS y MEDIAS

CALCINACIN

MEZCLA de oxidos con 45%Sm 29%Gd 13%Eu 6%Nd

PRECIPITADO FILTRADO COSTE 100 $/kilo VENTA Gd 4000 $/kilo

SEPARACION MAGNETICA

ESQUEMA UNIDAD BASICO DE EXTRACCION

VISION EXTRACCION A CONTRACORRIENTE

UNIDAD DE SEPARACION POR DECANTACION


REBOSE DE DISOLVENTE

AGITADOR

NIVEL DE REBOSE

DISOLVENTE+TR

CAMARA DE MEZCLA

ENTRADA

SOL. ACUOSA

PLANTA PILOTO DE MOLIENDA Y PLANTA DE EXTRACCION CON DISOLVENTES

REACCIONES DEL PROCESO


REACCION 1 : DESTRUCCION DEL FOSFATO (TR)3 PO4 + 3NaOH PO4Na3 + 6(TR)OH3

REACCION 2 : DISOLUCION DEL HIDROXIDO TR(OH)3 + HNO3 TR(NO3)3 + 2 H2O

REACCIONES DEL PROCESO


REACCION 3: EXTRACCION SELECTIVA CON DISOLVENTE

TR 3+

+3 (C8H17O)2 PO2H

Gd ((C8H17O)2 PO2H)3 +3H


+

REACCION 4: RECUPERACION DE GD PRECIPITACION CON ACIDO OXALICO

3C2O4H2 + 2Gd ((C8H17O)2 PO2H)3 (C2O4)3Gd2 + 6 ((C8H17O)2 PO2H)3

REACCIONES DEL PROCESO


REACCION 5: CALCINACION
(C2O4)3Gd2 + CALOR 6CO2 + 2Gd

PROBLEMAS DE MANTENIMIENTO
Los problemas de mantenimiento del equipo son importantes ,formacin de incrustaciones,corrosin,formacin de fangos,subidas en la viscosidad del cido,inestabilidad en el proceso.

Mecanismos qumicos de la extraccin con disolventes


El descenso del volumen atmico de los lantnidos , conforme aumenta su nmero atmico ,produce un aumento del comportamiento como aceptor de electrones . Aquello elementos con menos tendencia por los aniones o por los electrones , son considerados ms bsicos. La Basicidad de los elementos ,est relacionada con su radio inico y es lo mas importante para la extraccin. Asimismo la energa de formacin de los complejos con los solventes organicos ,aumenta con el nmero atomico La basicidad determina ,la solubilidad relativa de las sales , la facilidad con que los oxyaniones (oxidos) se descomponen al calentar y la estabilidad de los complejos.

BASE DE LA EXTRACCION ESCOGIDA


La>Ce>Pr>Nd>Pm>Sm>Pu>Gd>Tb>Dy>Ho>Y>Er> Tm>Yb>Lu>Sc Esta escala es la base de casi todos los sistemas de separacion Cristalizacin fraccionada Tcnicas de intercambio inico

Tcnicas de Extraccin son Disolventes


Asimismo las tcnicas de oxidacin-reduccin tambien se clasifican segn la basicidad

Con lacontraccin de volumen atmico se produce un aumento de la acidez, o disminucin de la basicidad, que constituye base suficiente para la separacin selectiva. Las diferencias se exaltan a veces utilizando agente formadores de complejos, tales como complexonas y en general cidos hidroxo o aminocarboxilicos

Para la separacin se emplea la diferencia en la estabilidad de los complejos de las tierras raras adyacentes y para ello se utilizan los agentes quelantes.

Un quelato, se define como una combinacin de un ion metlico con una molcula orgnica (agente quelante) para formar una estructura en anillo.Los quelatos son un tipo especial de complejos ,pero que son mucho ms fuertes

. La diferencia en la estabilidad de los quelatos de dos tierras adyacentes es ms que la diferencia en la estabilidad de los complejos ordinario. Este principio se utiliza para superar, en cierta medida, las dificultades que se plantean en la separacin como resultado de la basicidad muy similar de los iones de tierras raras vecinas

Processing of rare-earth concentrates generally involves an initial cracking or leaching step to bring the elements into solution. This is followed by a number of separation stages, first to separate groups of elements (the lights from the heavies) and then to separate individual elements from each othe

The extraction of trivalent lanthanide with HDEHP is represented by M3+ + 3(HA)2 [M(HA2)3] + 3H+, (1) where M is lanthanide and actinide and HA represents HDEHP [3, 4] which forms dimer in organic solvent [5]. log D = logKex 3log[H+] + 3log[HA2]org, (2) Kex =[M(HA2)3]org[H+]3aq/[M3+]aq[(HA)2]3org, (3) D = [M]org/[M]aq, (4) where D and Kex are the distribution ratio and the extraction constant of the metal, respectively.

HDEHP (di-2-ethylhexylphosphoric acid) is one of the extractant molecules most intensively used in liquidliquid extraction systems With the introduction of lactic acid (LacH) concentrations of lanthanides (Ln3+-HDEHP-lactate the amount of lactate extracted is correlated with the concentration of Ln3+ general stoichiometry 1 : 2 : 1 (Ln3+ : HDEHP : lactate).

Condiciones de extraccion
1.5mol/l for HDEHP by amixtrue of 0.15mol/l DTPA-2mol/l lactic acid with pH 3.5 25. Counter-current cascade experiment results show that through seven stages extraction and two stages scrub 99.8% 0.3-0.5 mol/lHNO_3, 1.0 or1.5mol/l HDEHp-kerosene as organic phase.

OMNISCAN Gadodiamida
http://www.ismrm.org/special/EMEA2.pdf

MAGNETISMO DEL Gd
http://lecturedemo.ph.unimelb.edu.au/Electri city-Magnetism/Magnetic-properties-ofMatter/Eh-1-Curie-Point-of-Gadolinium/CuriePoint-Diagram

PROPIEDADES del GADOLINIO


http://lecturedemo.ph.unimelb.edu.au/ Electricity-Magnetism/Magneticproperties-of-Matter/Eh-1-Curie-Pointof-Gadolinium/Curie-Point-Diagram

REFRIGERACION MAGNETICA
Other Uses of Gadolinium: Magnetic Refrigerators Scientists who study gadolinium are constantly discovering and developing new applications for this element. One of the most promising new applications is the use of gadolinium for making magnetic refrigerators. In 2001 the Milwaukeebased Astronautics Corporation of America demonstrated the worlds first successful magnet refrigerator. Unlike traditional appliances that use ozone-depleting refrigerants and consume a lot of electricity, the magnetic refrigerator uses gadolinium metal and special magnets to achieve the cooling effect. As a result, the magnetic refrigerator requires minimal amount of electrical energy and causes little to no harm to the environment. The magnetic refrigerator works due to the special magnetic properties of gadolinium. This metal heats up when exposed to a magnetic field and cools down when the magnetic field is removed. By manipulating the magnetic field, scientists are able to achieve a significant cooling effect the main requirement for a working refrigerator. Scientists are currently working on perfecting gadolinium-based cooling technology so it can be used on a wider scale to make environment-friendly home refrigerators, air conditioning devices and cooling equipment for electronics.

http://www.mrteverett.com/Chemis try/pdictable/q_elements.asp?langu age=en&Symbol=Gd#Thermochemis try


Night-vision goggles require...gadolinium" 2

http://www.chemistryexplained.com/ elements/C-K/Gadolinium.html#b
Special gadolinium minerals called yttrium garnets are used in microwave ovens. http://en.wikipedia.org/wiki/Nd:YAG http://www.webelements.com/gadolinium/uses. html

The magnetron tubes of microwave ovens contain gadolinium yttrium garnets. http://en.wikipedia.org/wiki/Cavity_magnetron http://de.wikipedia.org/wiki/Magnetron

http://www.gallawa.com/microtech/m agnetron.html
Basic Magnetron Structure The nucleus of the high-voltage system is the magnetron tube . The magnetron is a diode-type electron tube which is used to produce the required 2450 MHz of microwave energy. It is classed as a diode because it has no grid as does an ordinary electron tube. A magnetic field imposed on the space between the anode (plate) and the cathode serves as the grid. While the external configurations of different magnetrons will vary, the basic internal structures are the same. These include the anode, thefilament/cathode, the antenna, and the magnets

Basic Magnetron Operation The theory of magnetron operation is based on the motion of electrons under the combined influence of electric and magnetic fields. For the tube to operate, electrons must flow from the cathode to the anode. There are two fundamental laws that govern their trajectory:The force exerted by an electric field on an electron is proportional to the strength of the field. Electrons tend to move from a point of negative potential toward a positive potential. Figure 3-A shows the uniform and direct movement of the electrons in an electric field with no magnetic field present, from the negative cathode to the positive anode. The force exerted on an electron in a magnetic field is at right angles to both the field itself, and to the path of the electron. The direction of the force is such that the electron proceeds to the anode in a curve rather than a direct path.

http://www.buzzle.com/articles/gadolinium-uses.html

What are the Uses of Gadolinium Many of us have heard that gadolinium plays a major role in MRI (magnetic resonance imaging) but we are not sure what is gadolinium used for in MRI scan. Actually, in MRI scans it acts a contrast agent. Medical professionals administer solution of gadolinium compounds intravenously through injections into the patients body. The solution then flows into the bloodstream and enhances internal structures of the body. As a result, identification of abnormal cell growths and tumors become a lot more easier. Thus MRI with contrast enables timely diagnosis of several serious health problems. This element is also used in other imaging devices such as X-ray machines. Besides these gadolinium uses in medical field, it is used in many other industries. It is used in nuclear reactor simply because it is an excellent neutron absorber. However, it cannot absorb neutrons for a long time. Hence, it is used for shutting down nuclear reactors for emergency purposes only. Gadolinium oxide is used in the making of phosphors which is required in television tubes, computer memory and compact discs. The magnetron tubes of microwave ovens contain gadolinium yttrium garnets. It is added in trace amounts in various metals like iron, chromium, etc. to increase their resistance towards heat and corrosion. Various gadolinium compounds act as catalysts for chemical reactions that are involved with production of petroleum and several synthetic products. Like any other rare earth elements, elemental gadolinium could be toxic in nature. Therefore, if you are handling the metal for any type of gadolinium uses, then it should be done with great care. Inhalation or ingestion of the gadolinium should be strictly avoided with suitable precautionary measures. When it is used in the body for medical purpose, then it stays in the body for a very short span of time. For this reason, for most people it is safe and no major gadolinium side effects are observed. Only in some rare cases, some serious health complications may arise. By Bidisha Mukherjee Last Updated: 10/5/2011

APLICACIONES
The traditional and relatively high-volume end-use sector for rare earths in cerium oxide polishing powders, remains strong since virtually all optical glass lenses (including those in many digital cameras) and glass display panels for computer monitors and television screens are polished to high specifications

APLICACIONES 2
The principal applications for rare-earth phosphors are in display screens (cathode ray, liquid crystal and plasma) and in low-energy fluorescent lighting tubes

APLICACIONES 3
Lanthanum-nickel-hydride batteries, which were rapidly replacing nickel-cadmium For hybrid vehicles, however, nickel-metal-hydride batteries remain the primary choice

APLICACIONES 4
Neodymium and lanthanum, and to a lesser extent cerium, are used in the ceramic insulating layers between the conductive metallic electrode layers of multilayer ceramic capacitors (MLCC). These are found in cell phones, laptop computers, cameras and automobile electronic controls (braking, suspension, navigation aids) which also depend on highintensity rare-earth magnets.

APLICACIONES 5
Magnetic refrigeration, based on the magnetocaloric properties of gadolinium in arc-welded alloys composed of gadolinium, silicon and germanium, is a relatively new development that may provide relatively high energy efficiency compared with conventional refrigeration systems and, also, the elimination of environmental effects associated with the use of chlorofluorocarbons or ammonia as heat-transfer fluids.

APLICACIONES 6
Small quantities of yttrium are used as dopants for synthetic crystalline materials, eg, yttrium aluminium garnets (YAG) and yttrium aluminium perovskites for lasers

APLICACIONES 7
Trains based on magnetic levitation (maglev) technology using neodymium magnets, have been opened in Shanghai to link the international airport and with

APLICACIONES 8
Solid oxide fuel cells utilise lanthanum manganite doped with rare earths for the cathode, and yttria-stabilised zirconia as the electrolyte. Potential applications include yttria-stabilised zirconia as an electrolyte film for fuel cells, and battery electrodes

APLICACIONES 9
Rothmans Benson and Hedges Inc to apply nano-cerium products to control the emission of smoke from cigarettes and cigarette papers

APLICACIONES 10
Scandium is used principally in aluminium alloys for sporting goods such as baseball bats and bicycle frames. Scandium alloys are not only stronger and more resistant to corrosion, but welds are also stronger

APLICACIONES 11
A pyrophoric mixed rare-earth alloy called Mischmetall (50% Ce, 25% La, 25% other light lanthanides) or misch metal is combined with iron to make flints for cigarette lighters

APLICACIONES 12
automotive catalysts where mixed zirconiumcerium oxides have greater thermal stability and the oxygen storage capacity is greater at higher temperatures