CN87100207A - Produce zirconium white by zircon - Google Patents

Abstract

A kind ofly produce zirconic method from zircon.Zircon decomposes through alkali, the washing silica removal, and product is through dissolving with hydrochloric acid, solution evaporation is concentrated into proportion 40B'e, free acidity 6-8NHCl, and the water with 0.5-2 times of volume dilutes concentrated solution then, add 1% polyacrylamide simultaneously, stir, silicon and other impurity are a flocks and separate out.The gained solution acidity is controlled at 1-6NHCl, with ketone or neutral Phosphorus or amine extractant extraction Fe ^{+ 3}, solution primary crystallization zirconium oxychloride after the extraction deironing, calcination becomes ZrO ₂ZrO wherein ₂Content＞97%, SiO ₂＜0.01%, Fe ₂O ₃＜0.008%.ZrO ₂Casting yield (industrial scale) 〉=75%.

Description

A kind ofly produce zirconic method from zircon.

Produce zirconium white by zircon, adopt alkali (NaOH or Na ₂CO ₃) when decomposing, the silicon major part in the zircon changes into water-soluble water glass, washing and it is separated with zirconium.A part of silicon then exists with the silicic acid form of many water-baseds.Not only can not the water flush away, and it is also coating zirconium, makes reaction product Na ₂ZrO ₃With a part of Zr(OH) ₄Be difficult for precipitation, cause filtration difficulty, reduced the yield of zirconium.For removing this a part of silicon, generally adopt strong sulfuric acid response (200 ℃), make the silicic acid high temperature dehydration, flocking settling removes by filter; Perhaps use hydrochloric acid reaction (80 ℃), make zirconium become the solubility zirconates earlier, generate insoluble Zr(OH) again with the alkali neutralization ₄Precipitation makes silicon stay in the solution and remove by filter.Also have the silicon of some colloidal then also need add flocculation agent such as ox glue and help heavyly, remove by filter.In a word, produce in the zirconium white technology at the alkaline process decomposing zircon, the removal of silicon is time-consuming.

The removal of another impurity iron after zircon alkali decomposes is also very difficult, and is in sulphuric acid soln, general earlier with Fe ^{+ 3}Be reduced into Fe ^{+ 2}, then at P ^HZr water is situated between generates the Zr precipitation.Fe ^{+ 2}Then stay in the solution and remove by filter.In hydrochloric acid soln, also be with Fe ^{+ 3}Be reduced into Fe ^{+ 2}And it is isolating with Zr.Even like this, still some iron need pass through the zirconium oxychloride recrystallization, comprises with containing the qualified hydrochloric acid wash crystallization of Fe removing Fe, makes ZrDCl at last ₂8H ₂O calcination gained ZrO ₂In Fe ₂O ₃Content≤0.05% reaches technical grade ZrO ₂Standard.

Owing to produce in the zirconic alkali decomposition process flow process at zircon, remove the impurity ferrosilicon and all adopt precipitation, to clean, filtering method increases technical process, and is time-consuming.For this reason, invented zircon stone and decomposed through alkali, the solid product behind the washing silica removal once dissolves through hydrochloric acid, acid solution concentrates removes remaining silicon, acid solution is through a solvent extraction deironing behind the silica removal, gained water primary crystallization zirconium oxychloride, and directly calcination gets qualified ZrO again ₂Method.The inventive method is described in detail in detail below:

To contain ZrO ₂60% zircon and NaOH are mixed, ore: the NaOH(solid)=1: the 1.5(weight ratio), be warming up to 〉=800 ℃, and kept 2-3 hour, this moment, the zircon decomposition was complete substantially, then melts was poured in the cleaning barrels and was cleaned with hot water, to remove soluble silicon.Throw out Na ₂ZrO ₂Use industrial dissolving with hydrochloric acid, the elimination bits.Solution concentration to proportion is 4OBe ', free acidity 6-8NHCl.Then with the water dilution concentrated solution of 0.5-2 times of volume, add 1% polyacrylamide solution simultaneously and help heavyly, stir, silicon and other impurity are a floss precipitation, filter and remove.The solution of gained utilizes solvent-extracted method that Fe is separated with Zr behind the concentrated silica removal.According to Fe under solution acidity 1-6NHCl and this acidity ^{+ 3}Partition ratio at organic phase and aqueous phase, select ketone (methyl iso-butyl ketone (MIBK) etc.) or neutral Phosphorus (tributyl phosphate; first base Ling acid diformazan heptyl ester for use, San Xin Ji Ling oxide compound etc.) or amine, comprise primary amine (Primene JM-T etc.), secondary amine (Amberlite LA-1 etc.), tertiary amine (trioctylamine, tri-iso-octylamine, N235 etc.) and quaternary ammonium salt (Aliquat336, N263 etc.) extraction agent be that organic phase is carried out extracting and separating.Extraction phase is than O/A=1/1-1/2(volume ratio).The water organic phase is pressed extraction phase than after mixing, and fully stirs, and stops to stir making water and organic phase layering.The Fe of aqueous phase ^{+ 3}Be extracted into organic phase and with the Zr phase-splitting.Extracting operation can be once also can be repeatedly, until raffinate aqueous phase Fe ₂O ₃/ ZrO ₂Content meets ZrO ₂Requirement.The aqueous phase extracted condensing crystal gets ZrDCl ₂8H ₂O, calcination gets ZrO ₂The chlorine of overflowing in the calcination absorbs to be handled.Organic phase after the extraction is removed Fe through washing ^{+ 3}, recirculation is used.

Above solvent extraction can only be removed Fe ^{+ 3}And at aqueous phase except Fe ^{+ 3}Outer Fe in addition ^{+ 2}For this reason, can before solvent extraction, use oxygenant earlier (as H ₂O ₂Deng) with Fe ^{+ 2}Be oxidized to Fe ^{+ 3}And extraction is removed; Also oxidizer Oxidation of Fe not ^{+ 2}, and Fe when utilizing the primary crystallization zirconium oxychloride ^{+ 2}Stay water and remove.

According to the inventive method, produce ZrO by the decomposition of zircon alkali ₂Shi Youguan intermediate product and ZrO ₂Ferrosilicon content is in the finished product:

Have suffered (industrial scale) ZrO in the technology ₂Casting yield 〉=75%.

Embodiment 1:

Contain 60%ZrO ₂Zircon, put into porcelain crucible, zircon after mixing with solid caustic soda: solid caustic soda=1: the 1.5(weight ratio).Arrive 〉=800 ℃ at the stove internal heating then, and kept 2 hours.Question response finishes, and gets a loose shape product.This product is poured cleaning barrels into, with 80-90 ℃ of hot wash three times, filters the industrial dissolving with hydrochloric acid of gained throw out.The hydrochloric acid consumption is 2 liters of hydrochloric acid of per kilogram zircon consumption.Elimination bits, solution are sent into and are concentrated into proportion 4OB ' e, free acidity 6-8NHCl in the vaporizer, be the water dilution of 0.5 times of concentrated solution with volume ratio then, add 1% polyacrylamide solution simultaneously, stir, the precipitation that the group of separating out is cotton-shaped, filter and the solution behind the silica removal, it mainly consists of:

ZrO ₂8/l, SiO ₂8/l, Fe ^{+ 3}+ Fe ^{+ 2}8/l acidity N

（1） 46.6 0.069 0.24 4.8

（2） 60.6 0.083 0.29 5.3

（3） 57.8 0.046 0.19 4.9

Embodiment 2:

Concentrate silica removal liquid by embodiment 1 gained, with the extraction of 100% methyl isobutyl ketone solution, compare O/A=1/1, at this moment Fe ^{+ 3}Partition ratio be 1-10, the partition ratio of Zr is 10 ^-3-10 ^-2, two-phase mixes, static layering, raffinate aqueous phase Fe ^{+ 3}+ Fe ^{+ 2}Content is 0.06-0.08 8/l.

Embodiment 3:

With embodiment 2.Use the 100%TBP(tributyl phosphate instead) be extraction agent, compare O/A=1/1, at this moment Fe ^{+ 3}Partition ratio be 10 ³-10 ₄, the partition ratio of Zr is 10 ^-1-10.Aqueous phase Fe behind the extraction equilibrium ^{+ 3}+ Fe ^{+ 2}Content is 0.02-0.048/l.

Embodiment 4:

With embodiment 2.Using N235 instead is extraction agent, wherein adds alcohol mixture, and kerosene is additive and thinner.Ratio is N235: alcohol mixture: kerosene=2: 2: the 3(volume ratio), compare O/A=1/2, balance aqueous phase Fe ^{+ 3}+ Fe ^{+ 2}Content is 0.02-0.04 8/l.

Reference

1, red smeltery, Shanghai: zirconium sponge production process disposal of waste gas, water and industrial residue test brief summary (internal report)

2, Wang Qiang: zirconium Shanghai science tech publishing house, 1961

Claims (3)

1, a kind ofly produce zirconic method from zircon, zircon decomposes through alkali, the washing silica removal, product dissolves through acid, the crystallization zirconium oxychloride, and calcination becomes zirconium white, the present invention is characterised in that washing silica removal after product concentrates silica removal behind dissolving with hydrochloric acid, solution solvent extraction deironing behind the silica removal.

2, claim 1 is described produces concentrated silica removal in the zirconium white method by zircon, it is characterized in that washing silica removal after product is concentrated into proportion 40B ' e behind dissolving with hydrochloric acid, free acidity is 6-8N, then with 0.5-2 times of volume water dilution concentrated solution, add 1% polyacrylamide solution simultaneously, stir, precipitation is separated out silicon.

3, claim 1 is described produces extraction deironing in the zirconium white method by zircon, it is characterized in that solution is water behind the silica removal to concentrate, water free acidity 1-6NHCl, with ketone or neutral Phosphorus or amine extractant is organic phase, the two-phase thorough mixing, layering, aqueous phase Fe ^{+ 3}Optionally be extracted into organic phase and separate with zirconium.