US1351091A - Method of obtaining zirconium oxid - Google Patents

Description

UNITED STATES PATENT OFFICE,

LOUISE. Burrow, or'nIAeAnA FALLS, nnwxonx, nssrenon TO THE TITANIUM ALLOY mmrrrno'runme COMPANY, or new Yonx, N. Y., A conrom'rrou or MAINE. L

' METHOD OF OBTAINING ZIRCONIUM OXID.

1,351,09 r specification of Letters Patent. Patented Aug. 31, 1920. No Drawing. Application filed September 24, 1919. Serial- No. 325,961. I To all whom it may concern: nonitrid; myvsuch products containing by Be it knownU that I,SLoUIs BARTON, a analysis, for example: citizen of the nited tates an a resident of Niagara Falls, in the colinty of Niagara 5 and State of New York, have invented cer- Silica to 60 tain new and useful Improvements in Iron "7- to Methods of Obtaining Zirconiu m Oxid, of 6; to which the followlng 1s a specification. Nitrogen 8.0 to 100 My invention relates to the obtaining of zirconium oxid from materials containing it, The product is particularly Well adapted as for example from such an ore as badto treatment by the subsequent steps of my deleyite, or from zircon (zirconium silicate), method because it difiers in some respects, in which it may be found, naturally, or othere. g. as regards the ease with which it is possiwise, commingled or associated with one or ble to crush, or mill it to even as fine as 350 16 more of such substances, orimpurities,unmesh, and also as regards its composition, desired for certain uses, as silica, alumina, as above indicated, from to me known previiron, titanic, or other oxids, etc. ous carbid or nitrid products obtainable by The objects of my invention comprise the otherwise than as above described proporprovision of methods whereby zirconium' tioning and smelting the charge.

2.0 oxid can be, as aforesaid, obtained with in- J I continue my gradual charging and smeltdustrially practicable speed, directness and ing until the crucible, or hearth, of the fureconomy, and of such purity and other desirnace is full, after which I allow the char e to able properties as to peculiarly adapt it for cool and solidify and then remove it om an opaquing' agent in the production of the furnace.

25 white enamels; also for use in high grade I next crush this product, or solidified refractories, pigments, alloys, zirconium melt, consisting preponderatingly of zircosa'lt's, etc. nium cyanonitrid, by aid of any appropriate My invention is practised as follows, viz: apparatus, such as a jaw crusher, or a rolls I bring the above referred to material, or and ball mill, or equivalent, capable of re- 30 ore, containing zirconium oxid into contact, ducing it to a condition of fine comminution. y as by mixing it, preferably preliminarily The degree of fineness varies as may be incrushed (except zircon),-to about one-half dicated by the purpose for which my final inch size, or smaller, with an oxid reducing zirconium oxidproduct isto be employed, agent, preferably a carbonaceous agent, such, but it-is usually preferable to have it so fine 35 for example, as coke, the respective proporas to pass through a 350 mesh screen.

I tions being, within "limits, variable as may My next ste' designed in aid of obtaining be indica'ted:for example, when coke is, my final resuiting zirconium oxidproduct employed I usually prefer a ratio of about in condition sufficiently purified of undesired 20 pounds of coke to 100'pounds of such an substances, such, particularly, as iron com- 40 ore as baddeleyite, or zircon. pounds, is to subject the above described I then charge the mixture gradually into finely ground material, composed largely, or

an electric arc furnace at temperature such preponderatingly, of zirconium c anonitmd,

as to decompose the oxid,-the rate of chargto the action of sulfate of an alkali metal,

ing depending upon the composition of the preferably a neutral sodium sulfate, such as 45 ore, its analysis, andthe nature of its above salt cake, or an acid sodium sulfate such as referred to impurities, etc. The best rate of niter cake. Ta this end I make a thorough charging is read'ly determined for a particumixture in the ratio approximately of 0.75% lar charge by a little experimentation and to 0.80% parts by weight of the sodium sulanalysis of the resulting produc fate to one part of the zirconium cyanoni- 50 The result, if the charging'b'e thus gradutrid. This mixture I charge into an 1ron vesally and properly made, will, for example sel, and heat until reaction between ingrediwhen zircon has been mixed with coke, be a: ents of the charge has been started, after roduct consisting largel if not essentially, which the heat of reaction will usually prove .)f what I believe to be esignatable, and is suflicient to melt the mixture andcomplete hereafter designated, as a zirconi cyathe operation. Thetlius occasioned reactions no acid, preliminarily to result in producing, in the charge, oxids of zirconium and of silicon respectively, in reduction of the. sodium sulfate to sodium sulfid, and in the sodium sulfid combining with 1ron present to form ferro-sodium sulfid.'

he lgnited charge I immediately discharge into water contained in a' vessel provided, preferably, with an agitator, and in which I lixiviate the material until its soluble salts, including the ferro-sodium sulfid, are dissolved. The undissolved residue, composed principally of zirconium oxid, settles quickly as a sediment so that I am able to decant the most part of the alkaline sulfid solution, and thus withdraw therefrom the said sediment or residue. The residue I then treat with dilute sulfuric, or other, acid of about 5% strength, as in a bath containing such acid, until the remaining iron compounds, if any, are dissolved. The undissolved residue, 2'. e. the aforesaid zirconium oxid, I then separate, as by filtration or otherwise, dry it, and finally calcine it at a red heat of from about 600 C. to 700 (1, thus producing my substantially pure zirconium oxid final product.

In cases involving treatment by 111 method of a material, or ore, exceptionally impregnated with such undesired substances as iron compounds and from which the highest possible gradeof zirconium oxid final product is, for special uses, required,

find it advisable, if not preferable, to, preliminarily to mixing it with the sulfate of the alkaline metal, treat my above described intermediate product, containing the zirconium cyanonitrid, with dilute sulfuric,

dissolve and remove the bulk of the iron present. I then wash the residue water, and thereafter mix it with the sulfate of the alkali metal, and, from then on, continue my operation as before described. I

-The intermediate products derived from this last described treatment of my first, above described, intermediate product, containing zirconium cyanonitrid, by a bath containing dilute sulfuric, or equivalent,

, my aforesaid treatment with the sulfate of 'the alkaline metal, are, in themselves, and without their treatment by other chemlcal reagents, useful for certain purposes. Their protection I am seeking through the medium of an application for patent other than this.

aving' now described my invention, what I claim as new and desire to secure by Letters Patent is the following, viz:

1. In obtaining zirconium oxid, from a subjecting the resulting product to the action of sulfate of an alkali metal.

2. In obtaining zirconium oxid from a material containing an undesired substance, the steps which consist in melting said material with a carbonaceous reducing agent to production of zirconium cyanonitrid; treating the resulting product to a bath containing a dilute acid; withdrawing the undissolved residue; and subjecting it to the action of sulfate of an alkali metal.

3. obtaining zirconiumoxid from a material containing an undesired substance, the steps which consist in melting said material with a carbonaceous reducing agent to production of zirconium cyanonitrid; subjecting the resulting product to the action of sulfate of an alkali metal, and thereafter dissolving remaining iron compounds in dilute acid.

4. The method of obtaining zirconium oxid, from a material containing an undesired substance, which comprises: melting said material with a carbonaceous reducing agent to production of zirconium cyanonitrid; subjecting the resulting product to the actlon of sulfate of an alkali metal; subjecting the resulting product to an aqueous bath; withdrawing from said bath its sediment, or undissolved residue; subjecting it to the action of another bath containing a dilute acid; separating from said last mentioned bath its undissolved residue; and calcining it. p

5. The method of obtaining zirconium oxid from a material containing an undesired substance, which comprises: melting said material with a carbonaceous reducing agent to production of zirconium cyanonitrld; treating the resulting product o a bath containing a dilute acid; withdrawing and washing the undissolvedresidue; subjecting said residue to the action of sulfate of an alkali metal; subjecting the resulting product to an aqueous bath; withdrawing from said bath its sediment, or undissolved residue; subjecting this last mentioned residue to the action of a bath containing a dilute acid; separating from said last mentioned bath its undissolved residue; and calcining it.

LOUIS E. BARTON. Witnesses:

TOM C. GRAHAM, CARL P. Rnrsre.