DE1567456A1 - Process for removing titanium and vanadium from phosphoric acid - Google Patents

Description

Dr.-lng. HAMS RUSCHKE 25. ΑΡΓ »1966

DipK-bg, rr * Z AOULAR PSt2

D 1405
Dr.K / i

THE DOW CHEMICAL COMPMY, Midland, Michigan / v.St.A.

Process for removing titanium and vanadium from phosphorus

acid

The invention relates to a method for removing titanium and vanadium from phosphoric acid. In particular, it concerns Process for removing titanium and vanadium from phosphoric acid, which was obtained by treating phosphate rock with an aqueous acid, releasing the phosphoric acid.

Phosphoric acid is a widely used technical one Chemical used both directly and in the form of salts or derivatives for the production of foodstuffs, pharmaceuticals, Used in drinks and other goods, where the purity of the acid is essential for its usability j is in trade. The naturally occurring phosphate rocks generally contain considerable amounts of impurities

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such as calcium, fluorine, iron, aluminum, silicon, arwen, Titanium, vanadium and others. The purification of phosphoric acid obtained from such rocks or ores by treatment with aqueous acids therefore requires a considerable amount of work and time, although if the impurities are not removed, the phosphoric acid obtained is of poor quality and cannot be used for many purposes is. Because of the difficulty and inconvenience of metal removal from such an acid, it becomes im generally used in its impure state in the manufacture of fertilizers, and it is not intended for use used for food, beverages or pharmaceuticals.

Many processes are known by which phosphoric acid can be obtained economically from phosphate rock, the phosphate-containing rock first being decomposed with aqueous hydrochloric acid, sulfuric acid or nitric acid. The phosphoric acid released is then extracted from the resulting aqueous liquid with a practically water-insoluble organic extractant. Finally, the phosphoric acid from the water-insoluble organic extractant by a liquid-Plüssig-Extraktioja is stripped with water to obtain aqueous phosphoric acid _s.

■■ ', r

This recovery process for phosphoric acid can be used in liohen oalciumphoaphathaltigen materials Terwendei; will.

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"Λ ~ 1587456

Of particular importance are the naturally occurring phosphate ores such as fluorapatite, chlorapatite, hydraxvapatite, carbapatite, pebble, brownstone and amblygonite, monazite _? Varisoite and Fairfieldite »This method is also applicable to leached zone ore and phosphate-containing iron ores, such as the mixed I ^ Or-apatite ores, as they are common in the states of the Rocky Mountains. The process of digestion and organic extraction generally gives a relatively pure phosphoric acid compared to the phosphoric acid obtained after the construction process by methods other than organic extraction. However, this relatively pure acid also contains titanium and vanadium in sufficient quantities that it is undesirable or unsuitable for many uses. There is therefore a need in the art for a method of removing titanium and vanadium from phosphoric acid.

The present invention provides such a method for removing titanium and vanadium from phosphoric acid, with a solution of phosphoric acid in one handy solution water-insoluble organic extractant is formed, which is characterized in that this solution with a aqueous solution of hydrogen peroxide is treated, whereupon the organic phase containing the phosphoric acid is left to separate from the aqueous phase, which the. · Contains titanium and vanadium, and the organic layer is separated from the aqueous layer. The procedure is

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especially favorable for a through treatment stan stone or ** erg with hydrochloric acid, sulfuric acid or nitric acid ** acid produced! phosphoric acid.

Attempts have already been made to use uutan and vanadin from acid-leached solutions of phosphate geettin tu remove · These attempts generally resulted in en.twt4e; r Extraction or precipitation of these metals for application * Dies © Attempts, however, have so far been unsuccessful found that if © the acid leached from phosphate rock in a practically insoluble matter organic extraction agent is included, they with tiner aqueous solution of hydrogen peroxide can be hehandej ^ t and then an organic phase and ^^ ijae ^, jj ^ s ## ige Phaee * The resulting aqueous phase contains practically all 3) itan and vanadium originally in the Phos ^ phosphoric acid were present.

It Mfepm practically all of the known water-insoluble organic extractants that were previously used for the extraction of phosphoric acid, according to the f ^ will. This includes Sri alkyl phosphate such as' f aliphatic © alcohols »such as amyl alcohol, butyl alcohol, alcohol or heptyl alcohol, cyclohexanol, cyclohexanone, methylcyclohexanol and methylcyclohexanone, methyl ethyl ketone, Bligig acid ethyl ester, EsBig acid methyl ester, diethyl ether, di-npropyl ether, Diisopropyl ether and amides, such as 2. B. -K »JT-Di-Ja- * '

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"butvioctanamld. Such extractants must be effective to be and to avoid inadmissible solvent losses, be practically insoluble in water. This includes

she
are that / not soluble in water than about 10 wt. -fo may be. These solvents can be used alone or in combination with a diluent such as toluene, varsol (a petroleum-hydrocarbon mixture), benzene, decane, mineral oils, xylene, kerosene, mesitylene or other diluents which are otherwise inert to the system.

It iorämTc ^^ tB ^ ti ^ ge solutions of hydrogen peroxide in a concentration between about 0.2 to about 30 G-ew .- $ H ₂ O _{2 can be used} ^to remove titanium and vanadium. However, in general concentrations between 0.25 and 3.0 wt% H ₂ O _{2 are} preferred. Below 0.2 fo the 'extraction is ineffective, and titanium and vanadium are incompletely removed. With aqueous solutions containing more than 3% by weight of H ₂ O ₂ , the hydrogen peroxide is extracted into the organic layer, which lowers the effectiveness of metal removal.

The contact between the aqueous Hr> 0 ₂ solution and the phosphoric acid-containing organic extractant may by any suitable means, "for example, stirring, agitating or Plussig-liquid extract ion, obtained Daa virtually complete removal of titanium and vanadium required volume ratio of aqueous water- '" from a given volume of a solution of a

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phosphoric acid obtained by the hate process in a practical water-insoluble organic extractant is between about 1:10 "to about 1:50, with a ratio of 1:20 Ms 1:30 is generally preferred. The necessary contact time between these solutions is of the extent and the effectiveness of the mixing depends, however, is a contact time between 5 and 30 minutes generally with a countercurrent extraction system which is about 1 to 6 theoretical Steps is equivalent, suitable.

After sufficient contact between the two lo ^ - sung is achieved by stopping the movement or by directing the mixed solutions into a calm one Zone reached a phase separation. Here, the purified phosphoric acid is in the organic phase and practically that Contains all titanium and vanadium in the aqueous phase. These phases or layers can be easily known according to Separate processes, for example by conventional decanting or by peeling off one or both layers from one continuous separator.

The water layer separated in this way contains some residual H ₉ O _{9 in} addition to the titanium and vanadium separated from the phosphoric acid. . _: -R

After treatment with the aqueous hydrogen peroxide and the separation of the organic schiotite obtained therefrom -

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keeps the righteous fhoaphorgäu-re göiöst in the Extraction agent * Bid Öwijmuiig άβϊ iättte YfiJ? $ Is mean by ltetrakticm or Wa & aMm äe.r e & g & fttge & esi achieved with water «SNibe.i goes Wi Efcospfcöffetoe in

¥ erf | Ltoea

the Verwematöög eiiiej? SatilttÄbydafoxydlöetöig as

Yö ^ ttiiMft ^ e "i" _f case "lat ^ iwMpitoafliöt ÄÄ vrUiisohte Eiidpi? 6ätikt 'äasstftlit * Mi Ü &gttttg' the attü in your omganimMn ExtratetiöÄgaiittil Haftft source of ger ^ i» IGTE ihosiJßOjeaäwe. Veffvrestäet vf ^ Eae "into ·· ■ besQ »Greed, if you do: gäms? ^ Wide tusgeeetst W03? A ttm as Enäp3? Oduct e; ia Derifät dea? FltosphoFalm ^ e gtt

Although the present method YQ ^ SiWgawe in is at .Räumtemp ratti-r and AtmQSphärendrttQk SUSG ^ ^ fütot aind such conditions for de "expiration iee erfaiw e.ß.s" iaht undbäßige Abände ^ uÄgett follows:? "Mim waehteiligen provided natürliöh , that the feiaperatur is not eo that the% Qg becomes iittstabil or with the or

^J iii game ..; t.

Phosphoric acid was produced by Ätiflösett voa ^ phosphate rock in an aemisoh from about '3 1 eiiier 13 "κ. · Salt satire and about 1.8 liters of water. After dey Mflös ^ g des In the acid of Ötstein, the material became the material a small amount of an imlo-SÜehem ßUck & taiides filtered.

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1ü74li

r. 8th-

An analysis showed that the contribution was 16 yen _? 8 ^

24.7 tfew? - $ öhlqrid and $ 12.6 0alpium. A part of the material was then given with 3 YplUiflen # ί秧 & gi8i§8fe§§ iffi V ratio 50; 50, to the volume
And yarspl (an aliphatiimpftei3 EEdg

eztrahisyli · Bin! part of the dafte y

PljQrsäure und organisoiipiii Egtsaktjpnsmittel · (@ 5 φ§ΐ1§) with 1 yolumentein. a§B 1 ^ ig
§TQffperp3fyd kontaktiep- |, The

was prreiolit _f inde.m äiepe im ^ ggng ^ pm dyrpji eii | § irpn 6 idisc ^ -AtiBetE] 2ehäl.t§i? n wu ^ iä ^ i -Die. then overlong the separation, and the V / apgeypiia of the organic phase deducted, The water phfise fine straw yellow color due to the presence γόη φΐΐ & η. Vanadium in the complex with hydrogen peroxide, ÖJie ayf thus treated mixture of LosungSWi ^ tPl was enteric gewasphen with 3 parts Wasper, wpfeßi §ißh i ßohieht with 25 £ ew. * $ Phosphorus acid revealed The gäur§§ ß separated and contained 8 ppfii titanium and less ppm yana (iin _t

A second? The rope is made entirely of organic matter and phosphoric acid. treated with wa. 3 Wasppr was added to 25 parts of this M & tePta ·! P WU? ħn, whereby slph formed a Phpsphprg & ure§gi ioM which contained 25 wt .- ^ Phosphprs ^ acid »iia§h # § ^ contained dispe nipht treated ©

BAU OfMQINAL

phosphoric acid 50 ppm titanium and 5 ppm vanadium.

Other parts of the solution of organic extractant and phosphoric acid were different in the same way Treated concentrations of hydrogen peroxide in water. The following results were obtained:

Wt . Fo HpO ₂ . Ti + Y in the treated solution

in water . from solvent and acid (ppm)

QfO-S .. '. _L 7.1

0.1. . ,. 4.0

0.25. ■ ....- ■ ·, ..., 1.2 ■

0.50. ...... 1.1

1.0 1.0

2.0 '1.9

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Claims (4)

Claims 1.) Process for removing titanium and vanadium from Phosphoric acid, being a solution of phosphoric acid in a practically water-insoluble organic extractant is formed, characterized in that this solution with an aqueous solution of hydrogen peroxide is brought into contact, the organic phase containing the phosphoric acid formed by the The aqueous phase containing the titanium and vanadium is left to separate and the organic layer is separated from the aqueous layer. 2.) Process according to claim 1, characterized in that the hydrogen peroxide is in the form of an aqueous solution 0.2 to 30 wt .- $ is used. 3.) The method according to claim 1 or 2, characterized in that the ratio of the hydrogen peroxide solution to the Solution in the organic extractant between 1j10 and 1:50 lies. 4.) Process according to claim 1 to 3 _t daduroh characterized in that a trialkyl phosphate is used as the organic extractant. 009832 / U71