PL147224B2 - Method of obtaining pure lentanum ultraphosphate in crystalline form - Google Patents

Method of obtaining pure lentanum ultraphosphate in crystalline form Download PDF

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PL147224B2
PL147224B2 PL26111286A PL26111286A PL147224B2 PL 147224 B2 PL147224 B2 PL 147224B2 PL 26111286 A PL26111286 A PL 26111286A PL 26111286 A PL26111286 A PL 26111286A PL 147224 B2 PL147224 B2 PL 147224B2
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temperature
lanthanum
ultrafosphate
phosphate
crystals
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PL26111286A
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PL261112A2 (en
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Przedmiotem wynalazku jest sposób otrzymywania czystego ultrafosforanu lantanu w postaci krysztalów stosowanego w technice oswietleniowej jako luminofor oraz w technice laserowej.Znany jest przyklad z Journal of American Ceramic Soc. vol. 67 nr 1, 1984, sposób otrzymy¬ wania krystalicznego ultrafosforanu lantanu polegajacy na reakcji 85% H3PO4 z tlenkiem lantanu uzytym w ilosci 1 g. Porces trwa 10 dni w temperaturze 400-500° i przebiega w tyglach wykladanych szklistym weglem. Wadami metody sa: mala wydajnosc spowodowana tworzeniem sie produktów ubocznych (polikwasów) oraz wysoki koszt (tygle wykladane masa szklista).Sposób wedlug wynalazku polega na tym, ze tlenkowe polaczenia lantanu o wzorze NaLa02 uzyskane w wyniku ogrzewania równomolowej mieszaniny Na2CC3 i La203 w temperaturze okolo 573 K w ciagu 1 godziny poddaje sie reakcji z fosforanem dwuwodoroamonowym. W odmianie wynalazku mozna do równomolowej mieszaniny Na2C03 i La203 bezposrednio wprowadzic NH4H2PO4. Nastepnie prowadzi sie reakcje pomiedzy NaLa02 i fosforanem dwuwodoroamono¬ wym uzytymi w stosunku masowym 1:20 w temperaturze od 453 do 493 K w ciagu maksymalnie 1 godziny, po czym temeprature podwyzsza sie do wartosci od 673 do 823 K utrzymujac ja przez 2 godziny. Po tym czasie produkt w postaci monokrysztalów ultrafosforanu chlodzi sie i przemywa woda. Reagenty dogrzewa sie do temperatury 453-M93 K do temperatury 673-^-823 K z szybkoscia 10 K/min lub 5 K/godz., uzyskujac zaleznie od tego, mniejsze lub wieksze krysztaly.Sposób wedlug wynalazku daje mozliwosc skrócenia i uproszczenia procesu otrzymywania czystych krysztalów ultrafosforanu lantanu prowadzonego w fazie stalej oraz z tanich, dostepnych surowców.Przyklad I. Tlenowe polaczenie lantanu o wzorze NaLa02 otrzymano przez ogrzewanie w temperaturze 573 K 106 g Na2CX3 i 325,82 g LaaOs w ciagu 0,5 godz. 0,5 g uzyskanego produktu roztarto w mozdzierzu z 10,614 g NH4H2PO4. Roztarta mieszanine umieszczono w tyglu platyno¬ wym i ogrzewano w piecu kontaktowym z szybkoscia 10 K/min. Mieszanine utrzymywano w temperaturze 453 K przez okres 20 minut, a nastepnie dogrzewano do temperatury 823 K z szybkoscia 10 K/min. W tej temperaturze pozostawiono tygiel przez 1 godz. Po tym czasie 3,2 g2 147 224 produktu w postaci monokrysztalów LaPsOi4 o wymiarze 2 mm chlodzono, przemywano pieciok¬ rotnie woda i suszono. Analiza rentgenograficzna i spektroskopowa IR nie wykazaly obecnosci innych fosforanów w produkcie.Trzykladll.Wmozdzierzu roztarto 1,06 g Na2C03 oraz 3,2586 g La203 i 100 g NH4H4PO4.Calosc umieszczono w tyglu platynowym i ogrzewano w ciagu 30 minut w temperaturze 453 K. Z kolei podnoszono temperature do 823 K z szybkoscia 5 K/godz przez okres trzech dni. Docelowa temperature utrzymywano przez 2 godziny. Otrzymano 26,7 g ultrafosforanu lantanu LaPsO-u w postaci krysztalów o wymiarze 5 mm, które chlodzono, przemywano 5 krotnie woda i wysuszono.Zastrzezenia patentowe 1. Sposób otrzymywania czystego ultrafosforanu lantanu w postaci krysztalów polegajacy na reakcji zwiazków lantanu z fosforanem dwuwodoroamonowym w podwyzszonej temperaturze, znamienny tym, ze równomolowa mieszanine weglanu sodu i tlenku lantanu ogrzewa sie w tempera¬ turze okolo 573 K w ciagu 1 godziny, a uzyskany produkt poddaje sie reakcji z fosforanem dwuwodoroamonowym w stosunku molowym 1:20, w temperaturze od 453 do 493 K w ciagu maksymalnie 1 godziny, po czym temperature podwyzsza sie do wartosci 673 K do 823 K i utrzymuje ja w czasie maksymalnie 2 godzin, a nastepnie produkt w postaci monokrysztalów ultrafosforanu lantanu chlodzi sie i przemywa woda. 2. Sposób wedlug zastrz. 1, znamienny tym, ze reagenty ogrzewa sie z szybkoscia 10 K/min lub 5 K/godz. w zakresie temperatur od 493 do 823 K. 3. Sposób otrzymywania czystego ultrafosforanu lantanu w postaci krysztalów polegajacy na reakcji zwiazków lantanu z fosforanem dwuwodoroamonowym w podwyzszonej temperaturze, znamienny tym, ze do równomolowej mieszaniny Na2C03 i La2Co3 wprowadza sie bezposrednio fosforan dwuwodoroamonowy w stosunku masowym 1:20 i prowadzi reakcje w temperaturze od 453 do 493 K w ciagu maksymalnie 1 godziny, po czym temperature podwyzsza sie do wartosci od 673 do 823 K utrzymujac ja w czasie maksymalnie 2 godzin, a nastepnie produkt w postaci monokrysztalów ultrafosforanu lantanu chlodzi sie i przemywa woda. 4. Sposób wedlug zastrz. 2, znamienny tym, ze reagenty dogrzewa sie z szybkoscia 10 K/min lub 5 K/godz. w zakresie temperatur od 493 do 823 K.Pracownia Poligraficzna UP PRL. Naklad 100 egz.Cena 400 zl PLThe subject of the invention is a method for obtaining pure lanthanum ultrafosphate in the form of crystals used in the lighting technique as a phosphor and in laser technology. An example is known from the Journal of American Ceramic Soc. vol. 67 No. 1, 1984, a method for the preparation of crystalline lanthanum ultrafosphate consisting in the reaction of 85% H3PO4 with 1 g of lanthanum oxide. The process lasts 10 days at 400-500 ° and takes place in crucibles lined with glassy carbon. The disadvantages of the method are: low efficiency due to the formation of by-products (polyacids) and high cost (crucibles lined with glassy mass). The method according to the invention consists in the fact that the oxide lanthanum compounds of the formula NaLaO2 obtained by heating an equimolar mixture of Na2CC3 and La2O3 at a temperature of approx. 573 K is reacted in 1 hour with dihydroammonium phosphate. In a variant of the invention, NH4H2PO4 can be introduced directly into an equimolar mixture of Na2CO3 and La2O3. Subsequently, reactions between NaLaO 2 and the dihydrogen phosphate used in a mass ratio of 1:20 are carried out at a temperature of 453 to 493 K for a maximum of 1 hour, and the temperature is increased to a value of 673 to 823 K for 2 hours. After this time, the product in the form of single crystals of ultaphosphate is cooled and washed with water. The reactants are heated to the temperature of 453-M93 K to the temperature of 673 - ^ - 823 K at a rate of 10 K / min or 5 K / h, obtaining, depending on that, smaller or larger crystals. The method according to the invention allows for shortening and simplifying the preparation process pure crystals of lanthanum ultrafosphate carried out in the solid phase and from cheap, available raw materials. Example I. An oxygen combination of lanthanum with the formula NaLaO2 was obtained by heating at 573 K with 106 g of Na2CX3 and 325.82 g of LaaOs for 0.5 hours. 0.5 g of the product obtained was triturated in a mortar with 10.614 g of NH4H2PO4. The ground mixture was placed in a platinum crucible and heated in a contact furnace at a rate of 10 K / min. The mixture was kept at 453 K for a period of 20 minutes and then heated to 823 K at a rate of 10 K / min. The crucible was left at this temperature for 1 hour. After this time, 3.2 g of 2 mm LaPsOi4 monocrystalline product were cooled, washed five times with water and dried. X-ray analysis and IR spectroscopy showed no presence of other phosphates in the product. Example III. In the sander, 1.06 g of Na2CO3 and 3.2586 g of La2O3 and 100 g of NH4H4PO4 were ground. The whole was placed in a platinum crucible and heated for 30 minutes at 453 K. in turn, the temperature was raised to 823 K at a rate of 5 K / h for a period of three days. The target temperature was maintained for 2 hours. 26.7 g of LaPsO-u lanthanum ultrafosphate were obtained in the form of 5 mm crystals, which were cooled, washed 5 times with water and dried. Patent claims 1. The method of obtaining pure lanthanum ultrafosphate in the form of crystals by reacting lanthanum compounds with dihydro shammonium phosphate in the form of temperature, characterized in that an equimolar mixture of sodium carbonate and lanthanum oxide is heated at a temperature of about 573 K for 1 hour, and the obtained product is reacted with dihydroammonium phosphate in a molar ratio of 1:20 at a temperature of 453 to 493 K for a maximum of 1 hour, after which the temperature is raised to 673 K to 823 K and is maintained for a maximum of 2 hours, then the product in the form of lanthanum ultrafosphate single crystals is cooled and washed with water. 2. The method according to claim The process of claim 1, wherein the reactants are heated at a rate of 10 K / min or 5 K / h. in the temperature range from 493 to 823 K. 3. The method of obtaining pure lanthanum ultrafosphate in the form of crystals, consisting in the reaction of lanthanum compounds with dihydroammonium phosphate at elevated temperature, characterized in that an equimolar mixture of Na2CO3 and La2Co3 is directly introduced into dihydroammonium phosphate in a mass ratio of 1 : 20 and reacts at a temperature of 453 to 493 K for a maximum of 1 hour, after which the temperature rises to a value of from 673 to 823 K for a maximum of 2 hours, then the product in the form of lanthanum ultrafosphate single crystals is cooled and washed water. 4. The method according to p. The process of claim 2, characterized in that the reactants are heated at a rate of 10 K / min or 5 K / h. in the temperature range from 493 to 823 K. Pracownia Poligraficzna UP PRL. Mintage 100 copies Price PLN 400 PL

Claims (4)

Zastrzezenia patentowe 1. Sposób otrzymywania czystego ultrafosforanu lantanu w postaci krysztalów polegajacy na reakcji zwiazków lantanu z fosforanem dwuwodoroamonowym w podwyzszonej temperaturze, znamienny tym, ze równomolowa mieszanine weglanu sodu i tlenku lantanu ogrzewa sie w tempera¬ turze okolo 573 K w ciagu 1 godziny, a uzyskany produkt poddaje sie reakcji z fosforanem dwuwodoroamonowym w stosunku molowym 1:20, w temperaturze od 453 do 493 K w ciagu maksymalnie 1 godziny, po czym temperature podwyzsza sie do wartosci 673 K do 823 K i utrzymuje ja w czasie maksymalnie 2 godzin, a nastepnie produkt w postaci monokrysztalów ultrafosforanu lantanu chlodzi sie i przemywa woda.Claims 1. A method for obtaining pure lanthanum ultrafosphate in the form of crystals by reacting lanthanum compounds with dihydroammonium phosphate at elevated temperature, characterized in that an equimolar mixture of sodium carbonate and lanthanum oxide is heated at a temperature of about 573 K for 1 hour, and the product obtained is reacted with the dihydroammonium phosphate in a molar ratio of 1:20 at a temperature of 453 to 493 K for a maximum of 1 hour, after which the temperature is raised to 673 K to 823 K and maintained for a maximum of 2 hours, then the product, in the form of single lanthanum ultrafosphate crystals, is cooled and washed with water. 2. Sposób wedlug zastrz. 1, znamienny tym, ze reagenty ogrzewa sie z szybkoscia 10 K/min lub 5 K/godz. w zakresie temperatur od 493 do 823 K.2. The method according to claim The process of claim 1, wherein the reactants are heated at a rate of 10 K / min or 5 K / h. in the temperature range from 493 to 823 K. 3. Sposób otrzymywania czystego ultrafosforanu lantanu w postaci krysztalów polegajacy na reakcji zwiazków lantanu z fosforanem dwuwodoroamonowym w podwyzszonej temperaturze, znamienny tym, ze do równomolowej mieszaniny Na2C03 i La2Co3 wprowadza sie bezposrednio fosforan dwuwodoroamonowy w stosunku masowym 1:20 i prowadzi reakcje w temperaturze od 453 do 493 K w ciagu maksymalnie 1 godziny, po czym temperature podwyzsza sie do wartosci od 673 do 823 K utrzymujac ja w czasie maksymalnie 2 godzin, a nastepnie produkt w postaci monokrysztalów ultrafosforanu lantanu chlodzi sie i przemywa woda.3. A method of obtaining pure lanthanum ultrafosphate in the form of crystals based on the reaction of lanthanum compounds with dihydroammonium phosphate at elevated temperature, characterized in that an equimolar mixture of Na2CO3 and La2Co3 is directly introduced with dihydroammonium phosphate in a mass ratio of 1:20 and the reactions are carried out at a temperature of 453 to 493 K in a maximum of 1 hour, after which the temperature rises to a value of 673 to 823 K for a maximum of 2 hours, then the product in the form of lanthanum ultrafosphate single crystals is cooled and washed with water. 4. Sposób wedlug zastrz. 2, znamienny tym, ze reagenty dogrzewa sie z szybkoscia 10 K/min lub 5 K/godz. w zakresie temperatur od 493 do 823 K. Pracownia Poligraficzna UP PRL. Naklad 100 egz. Cena 400 zl PL4. The method according to p. The process of claim 2, characterized in that the reactants are heated at a rate of 10 K / min or 5 K / h. in the temperature range from 493 to 823 K. Printing Office of the UP PRL. Mintage 100 copies. Price PLN 400 PL
PL26111286A 1986-08-21 1986-08-21 Method of obtaining pure lentanum ultraphosphate in crystalline form PL147224B2 (en)

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