PL4947B1 - A method for dissolving a mixture of hafnium and zirconium phosphates and separating hafnium from zirconium. - Google Patents

A method for dissolving a mixture of hafnium and zirconium phosphates and separating hafnium from zirconium. Download PDF

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Publication number
PL4947B1
PL4947B1 PL4947A PL494725A PL4947B1 PL 4947 B1 PL4947 B1 PL 4947B1 PL 4947 A PL4947 A PL 4947A PL 494725 A PL494725 A PL 494725A PL 4947 B1 PL4947 B1 PL 4947B1
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Poland
Prior art keywords
hafnium
zirconium
mixture
acid
solution
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Application number
PL4947A
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Polish (pl)
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Publication of PL4947B1 publication Critical patent/PL4947B1/en

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Niniejszy wynalazek odinosi sie do sposobu rozpuszczania fosforanów hafnu i cyrkonu i oddzielania w otrzymanym roz¬ tworze hafnu od cyrkonu.Podlug /wynalazku niniejszego sposób ten moze polegac na tern, ze miesizantime fo¬ sforanów hafnu i cyrkonu rozpuszcza sie w osradku, zawierajacym wolny kwais szczawiowy, stezony kwas siarkowy lub kwas fosforowy. Osrodek, zawierajacy wol¬ ny kwas szczawiowy, moze njp. skladac sie z roztworu kwasu szczawiowego lub z roz¬ tworu szczawianiów z taka iloscia kwasu, ze kwas szczawiowy zastaje uwolniony, Z otrzymanego roztworu soli hafnu i cyrkonu mozna podlug wynalazku niniej¬ szego zapomoca zasady lub cial, posiada¬ jacych odczyn zasadowy o wystarczajaco wysokiej koncentracji jonó^w wodorotleno¬ wych, wytracic tlenki hafnu i cyr|konu.Celem rozdzielenia mieszaniny 'zwiaz¬ ków hafnu i cyrkonu podlug wynalazku ni¬ niejszego uzywa sie, jako produktu wyj¬ sciowego, roztworu mieszaniny fosforanów hafnu i cyrkonu w osrodku, zawierajacym wolny kwas iszczawiiowy, (stezony kwais siar¬ kowy lub kwais fosforowy. Roztwór ten mczna rozdzielic pcdlu|g wielu znanych me- rtod. Wedlug wynailaizku niniejszego otrzy¬ muje sie bardzo korzystne wyniki przez poddanie tego roztworu frakcjonowanemu stracaniu; celowem ijcslt podlug niniejszego wynalazku uzyc do tejgo, stracania kwasu solnego.?, Ni^^^pic^e:, ^zyjktaidy wykpnanla sjtiza dla blizaa^cy wyjasnieiii ninie^ze- 3ez^::^;l.:^meak^ miieszaawiy - fasfo* .^^¦.¦Lffeu!;! cyrkonu, zawierajacej okolo 2£:4.|^ta^J^^^^d^^ do nasyconego rciz^cttu kwgstt^^lzcz-awiow-egoi, Wtedy oka- myei.-sft), zepaltem uzyc 1,5 1 tego roztwo¬ ru do rozpu^zczjenia zawiesiny fosfora¬ nu. 100 cm3 izawfesiny iriiesizaiiiny fosfora¬ nów Laffiu ii ewtyoftiii, izaWeraj acetf okolo Pi6 g metalu,^roapuszcza siie zu|peilinie ipo dod&niw 20Q eta3 sitaizotne^o kwasu siatko¬ wego* s VY- W podobny siposób iniozina zupelnie - raz- puscic lOfr cm3 zawiefshry mieszaniny fo¬ sforanów hafniu i cyrkonu, zawiierajace;j o- kolo 0,6 £ metalu przez dodanie 300 clm3 kwasu fosforowego o ciezarze wlasdtwytm 1,75.Jezeli tak otrzymany rozlfwór wleje sie do tak wielkiej ilosci roztworu zasady, ze¬ by plyn az do konca tej operacji posiadal odczyn alkaliczny, wtedy otrzyma sie osad m/ieszaniiny tlenków hafnu i cyrkonu; Jesli 100 cm3 zawidsiny imlieszaniny fosforanów hafnu i cyrkonu, zawierajacej w stosunku do cyrkonu 4% hafnu, mozpusci sie w 200 cm3 stezonego kwasu siarikoweigo i do tak otrzymanego roztworu, wykazu¬ jacego ciezar wtasdWy 1,68, doda sie 30 om3 wody, itd po, kilku dtiiadh wydzieli sie osad. Olkazujie sie, ze^sad ten zawiera 10% hafnu W stosunku do cyrkonu. Po dodaniu do pozioistale^o roztworu dalszych 30 cm3, okazuje sie, ze osadf, który teraz o^ada, zawiera 6% hafnu w stosunku do cyrkonu.Clelzar wlasciwy roztwfo^u spadl w tym czasie dio 1,48. Po mzcfeAcizeniu! tego roz¬ tworu .rówttia objetoscia wody dkaizuje sie, ze utworzony psad zawiera tylko 2% haf¬ nu w stosunku do cyrkonu. Dalej' okazuje sie, ze osad, który otrzymuje sie przez (stra¬ cenie pozostalego roztworu pfrzy pomocy sodfy ztfacefi, fast woliny od htafnul A Jezelli rozpuscic pewna ilosc mielszalni- ny fosforanów hafnu i cyrkonu, zawieraj a- oej mniej' wiecej 4% hafnu w stopunku do cyrfcomi^ w 24 1 kwasu szczawiowego, to mo&na wytracic ten. roztwór czesciowa przy pomocy 2,5 1 steioinego kwasu solnego.Otrzymany osad odisisany rozpuszcza sie powtórnie w 5,5 1 kwasu szczawiowego, pocztem wytraca ,go sie powtórnie 2 1 kwasu aokuego. Raiz jeszcze rozpuszcza sie osad w 6 1 kwasu szczawiowego h wytraca 2 1 kwasu solniegjo. Wtedy o- kazuje siiej, ze otrzymany tak osad1 zawiera 30% hafnu w stosunku (do cyrkonu. Poste¬ pujac w opisany ^poisóib joszcze dWa razy, otrzyma sie osad zawierajacy 50% hafnu w sitosunjku do cyrkonu, a przy dluzszemi powtarzaniu tej metody, mozna afrzyittac osiald wykazujacy bardizo wysoka zawartosc hafnu.Zamiast stracania osadu zapomoca kwasu solnego, mozna stospwac jeszcze in¬ ne do tego celu prowadzace snodki, np. al¬ kohol, W wielu wypadkach mozna takze wytracac osad przez ogrzanie.Podczas gdy w dotychczas) opisanych przykladach o&iajgalo sie rozdzial izapoimo- ca frakc|joncwanqgo stracania* osadu, w mizej przytoczonym przykladzie oddziele¬ nie (polega na metodzie frakcjonioiwanej ekstrakc|ji. 100 cm3 zawiesiny mieszaniny fosfora¬ nów hafnu i'cyrkoniu, zawierajacej 4% hafnu, rozpuszcza sie czesciowo przy uzyciu 50 cm3 kwasu fosfaro(we|go o ciezarze wla¬ sciwym 1,75. Jezeli po przesaczeniu wy¬ traci sie iz tego, Roztworu wodorotlenek przez dodanie zasady, to ofcaize sie on praktycznie wolnym od hafnu. Jezefli pozo¬ stala zawiesine potraktowac po raz Wtóry kwasem fosforowym, wtedy okaze si^, ze otrzymany roztwór równiez jest ubogi w hafn, i ze ipozostala zawiesina zawiera znacznie wiecej, anizeli 4% hafnu w sto¬ sunku do cyrjkonu. — 2 — PLThe present invention relates to a method for dissolving hafnium and zirconium phosphates and separating hafnium from zirconium in the resulting solution. In the present invention, this method may be based on the fact that the mixture of hafnium and zirconium phosphates is dissolved in a precipitate containing free oxalic acid. , concentrated sulfuric acid or phosphoric acid. A medium containing free oxalic acid can, for example, consist of a solution of oxalic acid or an oxalate solution with such an amount of acid that the oxalic acid is released. From the resulting hafnium and zirconium salt solution, it is possible, in accordance with the present invention, to use bases or bodies having an alkaline reaction with a sufficiently high concentration ions of hydroxide ions, to eliminate the oxides of hafnium and zirconium. To separate the mixture of hafnium and zirconium compounds in the present invention, as a starting product, a mixture of hafnium and zirconium phosphates in a medium containing free Ischavic acid, (concentrated sulfuric acid or phosphoric acid. This solution is a solid mulch to separate a mixture of many known methods. According to the present invention, very favorable results are obtained by subjecting this solution to a fractionated loss; it is advisable to use it for the purpose of the present invention. this, the loss of hydrochloric acid.?, Ni ^^^ pic ^ e :, ^ zyjktaidy took out sjtiza for a close explanation of ^ s ^ s ^ :: ^; l .: ^ meak ^ miieszaawiy - fasfo *. ^^ ¦.¦Lffeu!;! zirconium, containing about £ 2: 4. | ^ ta ^ J ^^^^ d ^^ to saturated rciz ^ cttu kwgstt ^^ lzcz-aviow-egoi, then okammyei.-sft), zepaltem use 1.5 1 of this solution to dissolve the phosphate suspension. 100 cm3 of isavfesin, and of Laffiu phosphates and evophtophthies, and take acetf about Pi6 g of metal, it is drained, and after 20Q of sieve phase is added to retic acid * s VY- In a similar manner - dissipation a mixture of hafnium and zirconium phosphates containing about 0.6 £ of metal by adding 300 clm3 of phosphoric acid with a weight of 1.75. If the solution thus obtained is poured into such a large amount of alkali solution that the liquid is until the end of this operation it was alkaline, then a sediment of a mixture of hafnium and zirconium oxides will be obtained; If 100 cm3 of hafnium and zirconium phosphate mixture, containing 4% of hafnium in relation to zirconium, is allowed to settle in 200 cm3 of concentrated sulfuric acid and the solution thus obtained, showing its weight of 1.68, is added 30 ml of water, etc. , a few dtiiadh sediment will separate. It turns out that this orchard contains 10% of hafnium in relation to zircon. When a further 30 cm 3 was added to the horizontal solution, it appears that the precipitate which is now forming contains 6% of hafnium with respect to zirconium. The Clelzar proper solution has dropped to 1.48 during this time. After mzcfeAcizeniu! With this solution, it is proved that the psad formed contains only 2% of hafnium in relation to the zirconium. Further it turns out that the sediment which is obtained by (by wiping the remaining solution with the aid of sodfa ztfacefi, fast volts from hafnium and Jezelli dissolving a certain quantity of the millable hafnium and zirconium phosphates, contain as much as less than 4% of hafnium. in the process of cyrfcomy ^ in 24 l of oxalic acid, this can be precipitated. a partial solution with 2.5 l of stelin hydrochloric acid. The resulting sludge sucked off is re-dissolved in 5.5 l of oxalic acid, destroyed by post, it is repeated 2 l Raiz still dissolves the precipitate in 6 l of oxalic acid, and dissolves 2 l of hydrochloric acid. Then it turns out that the precipitate obtained in this way contains 30% of hafnium in relation to zirconium. , you will get a precipitate with 50% hafnium in the zirconium sieve, and if you repeat this method for a long time, you can get a sediment that shows a very high content of hafnium. Instead of losing the sediment with hydrochloric acid, you can use other In many cases, it is also possible to remove the sediment by heating. While in the examples described so far, there was a separation and the cooling of the fraction of ionic loss of the sediment, in the following example the separation (consists of on the fractionated extraction method. 100 cm3 of a suspension of a mixture of hafnium and zirconium phosphates, containing 4% of hafnium, is partially dissolved with 50 cm3 of phosphorus acid (fiber with a specific weight of 1.75. If, after filtering, either of this solution is lost. hydroxide by adding a base, it is formed practically free from hafnium.If the remaining suspension is treated again with phosphoric acid, it turns out that the obtained solution is also poor in hafnium, and that the remaining suspension contains much more than 4 % of hafnium to zirconium - 2 - PL

Claims (5)

Zastrzezenia patentowe. 1. Spoisób rozpuszczania mieszaniny fo¬ sforanów hafnu i cyrkonu, zmamienny tem, ze wprowadza sie wymienione sole hafnu i cyrkonu do osrodka, zawieraijaeego wo,lhy kwas szczawiowy, sitezony kwais siarkowy lub kwas fosforowy.Patent claims. 1. A process for dissolving a mixture of hafnium and zirconium phosphates, alternatively by introducing the said hafnium and zirconium salts into a medium containing water, lhydroxalic acid, sulfuric acid sitezones or phosphoric acid. 2. , Sposób wedlug zastrz. 1, znamienny tern, ze z roztworu wytraba sie przy pomo¬ cy zasady lub ciala o odczynie zasadowym dosc wysokiej koncentracji jonów woidoro- tilenowych mieszanine tlenków hafnu i cyr¬ konu.2., The method according to claim A method according to claim 1, characterized in that a mixture of hafnium and zirconium oxides is extracted from the solution by alkali or an alkaline body with a fairly high concentration of voidotilene ions. 3. Sposób oddzielania zwiazków hafnu od zwiazków cyrkonu, znamienny ,tein, ts jako produktu wyjsciowego uzytwa isie roz¬ tworu otrzymanego weidlug zastrz, 1,3. The method of separating hafnium compounds from zirconium compounds, characterized by tein, ts as a starting product of the use and the solution obtained from the material of claim 1, 4. Sposób wedlug zaistrz. 3, zSraamilenny /tern, ze oddzielenia (dokonywa isie przy po¬ mocy fraikqjonowatnego stracania osadu.4. The method according to the occurrence. 3, zSraamilenny / tern, from the separation (this is done by means of fractional sludge loss. 5. Sposób wedlug zaistrz. 4, znamielnny tern, ze osad straca sie kwasem isolnym, N. V. Philips, Gloeilampenfabrieken. Zasteipca: W, Suchowiak, rzecznik patentowy. Druk L. Boguslawskiego, Warszawa. PL5. The method according to the occurrence. 4, a significant area where the sediment becomes isolne acid, N. V. Philips, Gloeilampenfabrieken. Zasteipca: W, Suchowiak, patent attorney. Print by L. Boguslawski, Warsaw. PL
PL4947A 1925-05-18 A method for dissolving a mixture of hafnium and zirconium phosphates and separating hafnium from zirconium. PL4947B1 (en)

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