CN106395881B - Zirconium, hafnium, the method for calcium are removed from thick scandium oxide or scandium enriched substance - Google Patents
Zirconium, hafnium, the method for calcium are removed from thick scandium oxide or scandium enriched substance Download PDFInfo
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- CN106395881B CN106395881B CN201610858818.6A CN201610858818A CN106395881B CN 106395881 B CN106395881 B CN 106395881B CN 201610858818 A CN201610858818 A CN 201610858818A CN 106395881 B CN106395881 B CN 106395881B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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Abstract
Zirconium, hafnium, the method for calcium are removed from thick scandium oxide or scandium enriched substance, is comprised the following steps：(1) thick scandium oxide or scandium enriched substance are taken, strong acid is added, 60~100 DEG C of dissolvings is heated to, filters, scandium concentration is in 10~60g/L in control filtrate, and acidity is in 0.01~1mol/L；(2) temperature is maintained at 5~100 DEG C, under agitation, added into the filtrate handled through step (1) and remove zirconium, hafnium, calcium agent, after adding, boil, filtering, obtains filtrate, filtrate is being heated under the conditions of 60~100 DEG C, oxalic acid is added to be precipitated, precipitation is scrubbed to obtain oxalic acid scandium, and scandium oxide is made in the calcination at 750~850 DEG C of oxalic acid scandium.The zirconium in scandium feed liquid, hafnium, calcium can be reduced to several ppm using the present invention, the reaction time is short, easily filters, and scandium will not be caused damage, obtained scandium oxide purity is more than more than 99.95%.
Description
Technical field
The present invention relates to a kind of method that zirconium, hafnium, calcium are removed from thick scandium oxide or scandium enriched substance.
Background technology
Scandium oxide, metal scandium and its compound have many excellent characteristics, in fuel cell, Aero-Space, electronics etc.
Aspect is widely used.But because of rareness, extract extremely difficult, and scandium is generally associated resources, such as association is in ilmenite and zirconium English
Shi Zhong.Existing domestic big portion is to extract in scandium oxide and zirconium chloride spent acid to extract scandium oxide from titanium white waste acid, wherein mainly using
The impurity content such as titanium, iron, zirconium, hafnium, calcium is higher in extraction, but titanium white waste acid and zirconium chloride spent acid, and ferrotianium therein can pass through
Washing and oxalic acid precipitation and remove, because zirconium, hafnium, calcium influence, the total amount of obtained thick scandium oxide often 90% or so, wherein
Zirconium, hafnium, the content of calcium are 3%~10% or so, therefore pole is necessary to purify thick scandium oxide and scandium enriched substance.
The method of removal of impurities in existing thick scandium oxide, the Chinese patent application institute such as Application No. 201110099856.5 is public
Open《The method of separating zirconium and the preparation method of scandium oxide from the raw material of scandium-enriched》, this method is sour molten scandium-enriched raw material,
The one or more added after filtering in phosphoric acid, phosphate and mandelic acid, the zirconium in scandium oxide can be down to several by this method
Ppm, but this method is after adding except zirconium agent, and due to the characteristic of basic zirconium phosphate, precipitation particle is extremely tiny, it is difficult to filter, needs to add
Flocculant condenses precipitation, can just solve the problems, such as to wear filter, and it is serious otherwise to wear filter, and this method is compared with carrying out and add under peracid
The phosphate radical impurity for being difficult to decompose is entered, has caused in scandium oxide product that phosphate radical is too high, this method is only for single contaminant in addition
The removal of zirconium.Disclosed in the Chinese patent application of Application No. 201410809499.0《Separated from solution containing scandium except iron,
Aluminium, calcium, the method for titanium impurity》The impurity such as the impurity such as iron, aluminium, calcium and partial-titanium, zirconium, magnesium, manganese can be removed simultaneously there is provided one kind
Method, but this method uses ion-exchange, and time-consuming, efficiency is low, resin also needs regeneration.Application No.
201110186520.2 Chinese patent application disclosed in《A kind of purification preparation method of High-purity Sc Oxide》Disclose purification
The method of thick scandium oxide, this method is using sour molten-filtering-ammonia precipitation process-filtering-molten-filtering-ammonia precipitation process-filtering-of hypo acid again
The step of sour molten-oxalic acid precipitation, is purified, and step is various, and hydroxide filtration difficulty, and time-consuming.
The content of the invention
The technical problems to be solved by the invention be to provide it is a kind of easy to operate, and can be from thick scandium oxide or scandium enriched substance
In simultaneously remove product in zirconium, hafnium, three kinds of impurity of calcium, so as to obtain the method for high-purity mangesium oxide scandium product.
The technical solution adopted for the present invention to solve the technical problems is：From thick scandium oxide or scandium enriched substance remove zirconium,
The method of hafnium, calcium, comprises the following steps：
(1) thick scandium oxide or scandium enriched substance are taken, strong acid is added, is heated in 60~100 DEG C of dissolvings, filtering, control filtrate
Scandium concentration is in 10~60g/L (preferably 30~50g/L), acidity (" H+" concentration) in 0.01~1mol/L；
(2) temperature is maintained at 5~100 DEG C (preferably 20~50 DEG C), under agitation, to the filter handled through step (1)
Added in liquid and remove zirconium, hafnium, calcium agent, after adding, boiled, filtered, obtain filtrate, filtrate is being heated under the conditions of 60~100 DEG C, added
Oxalic acid is precipitated, and precipitation is scrubbed to obtain oxalic acid scandium, and oxidation is made in the calcination under 750~850 DEG C (preferably 800 DEG C) of oxalic acid scandium
Scandium.
Further, in step (1), the one or more of described strong acid in hydrochloric acid, sulfuric acid and nitric acid.
Further, in step (2), the added quality except zirconium, hafnium, calcium agent is zirconium oxide, hafnium oxide and calcium oxide in filtrate
1~2 times of quality sum.
Further, it is described except zirconium, hafnium, calcium agent are selected from o-iodobenzoic acid ammonium, o-iodobenzoic acid sodium and adjacent iodine in step (2)
One kind in Potassium Benzoate.
Further, in step (2), the temperature boiled is 100 DEG C, and the time boiled is 5~60min.
The zirconium in scandium feed liquid, hafnium, calcium can be reduced to several ppm using the present invention, the reaction time is short, easily filters,
And scandium will not be caused damage, obtained scandium oxide purity is more than more than 99.95%, while the present invention is in Low acid condition
Under, except complete zirconium, hafnium and calcium filtrate can direct oxalic acid precipitation, and it is very wide to be applicable zirconium, hafnium and calcium concentration scope, does not bring into or not is difficult to point
The impurity of solution, can significantly simplify technique and reduce cost.
Embodiment
The invention will be further described with reference to embodiments.
Embodiment 1
Take thick scandium oxide raw material 25g (Sc2O3：94.1%, ZrO2：4.725%, HfO2：0.945%, CaO：0.1%), plus
Enter 6mol/L hydrochloric acid 181ml, be heated to 80 DEG C of dissolvings, filtering, filtrate adds water and is diluted to 500ml, wherein, Sc2O3：47g/L,
ZrO2：2.36g/L, HfO2：0.4725g/L, CaO：0.05g/L, H+：0.1mol/L；Temperature is maintained at 20 DEG C, in stirring condition
Under, o-iodobenzoic acid ammonium is added (with 4wt% o-iodobenzoic acid ammoniums by 2 times of upper zirconium oxide, hafnium oxide and calcium oxide quality sum
The mode of solution is added), after adding, 10min is boiled at 100 DEG C, is filtered, mixing filtrate volume is 625ml, analyzes filtrate：
Sc2O3：37.63g/L, ZrO2：0.0001g/L, HfO2：0.00005g/L, CaO：0.0001g/L, filtrate is being heated to 100 DEG C
Under the conditions of, add oxalic acid and precipitated, precipitation is scrubbed to obtain oxalic acid scandium, and scandium oxide, oxygen is made in the calcination at 750 DEG C of oxalic acid scandium
Change scandium product analysis and the results are shown in Table 1.
Table 1
Embodiment 2
Take thick scandium oxide raw material 50g (Sc2O3：93.1%, ZrO2：5.7%, HfO2：0.98%, CaO：0.12%), add
4mol/L hydrochloric acid 550ml, are heated to 90 DEG C of dissolvings, and filtering, filtrate adds water and is diluted to 900ml, wherein, Sc2O3：52.833g/
L, ZrO2：3.167g/L, HfO2：0.544g/L, CaO：0.067g/L, H+：0.2mol/L；Temperature is maintained at 50 DEG C, in stirring bar
Under part, o-iodobenzoic acid sodium is added (with 6wt% o-iodobenzoic acids by 1.5 times of upper zirconium oxide, hafnium oxide and calcium oxide quality sum
The mode of sodium solution is added), after adding, 30min is boiled at 100 DEG C, is filtered, filtrate volume is 1080ml, filtrate is analyzed：
Sc2O3：43.889g/L, ZrO2：0.0011g/L, HfO2：0.0002g/L, CaO：0.0006g/L, filtrate is in 80 DEG C of heating condition
Under, add oxalic acid and precipitated, precipitation is scrubbed to obtain oxalic acid scandium, and scandium oxide, scandium oxide is made in the calcination at 800 DEG C of oxalic acid scandium
Product analysis the results are shown in Table 2.
Table 2
Embodiment 3
Scandium is taken to be enriched with raw material 100g (Sc2O3：21%, ZrO2：1.2%, HfO2：0.21%, CaO：0.03%), add
4mol/L hydrochloric acid 550ml, are heated to 100 DEG C of dissolvings, filter, filtrate volume is 500ml, wherein, Sc2O3：42g/L, ZrO2：
2.4g/L, HfO2：0.42g/L, CaO：0.06g/L, H+：0.01mol/L；Temperature is maintained at 50 DEG C, under agitation, by upper
1.3 times of addition o-iodobenzoic acid potassium of zirconium oxide, hafnium oxide and calcium oxide quality sum are (with 6wt% o-iodobenzoic acid potassium solutions
Mode add), after adding, 20min is boiled at 100 DEG C, filter, filtrate volume is 600ml, analyze filtrate：Sc2O3：
34.5g/L, ZrO2：0.0021g/L, HfO2：0.00045g/L, CaO：0.001g/L, filtrate adds at 90 DEG C of heating condition
Oxalic acid is precipitated, and precipitation is scrubbed to obtain oxalic acid scandium, and scandium oxide, scandium oxide product analysis is made in the calcination at 850 DEG C of oxalic acid scandium
It the results are shown in Table 3.
Table 3
Claims (4)
1. zirconium, hafnium, the method for calcium are removed from thick scandium oxide or scandium enriched substance, it is characterised in that comprise the following steps：
(1) thick scandium oxide or scandium enriched substance are taken, strong acid is added, scandium in 60~100 DEG C of dissolvings, filtering, control filtrate is heated to dense
Degree is in 10~60g/L, and acidity is in 0.01~1mol/L；
(2) temperature is maintained at 5~100 DEG C, under agitation, is added into the filtrate handled through step (1) and removes zirconium, hafnium, calcium
Agent, after adding, boils, filtering, obtains filtrate, filtrate is being heated under the conditions of 60~100 DEG C, adds oxalic acid and is precipitated, is precipitated
Scrubbed to obtain oxalic acid scandium, scandium oxide is made in the calcination at 750~850 DEG C of oxalic acid scandium；
It is described except zirconium, hafnium, calcium agent are in o-iodobenzoic acid ammonium, o-iodobenzoic acid sodium and o-iodobenzoic acid potassium in step (2)
It is a kind of.
2. according to claim 1 remove zirconium, hafnium, the method for calcium from thick scandium oxide or scandium enriched substance, it is characterised in that
In step (1), the one or more of described strong acid in hydrochloric acid, sulfuric acid and nitric acid.
3. according to claim 1 or 2 remove zirconium, hafnium, the method for calcium from thick scandium oxide or scandium enriched substance, its feature exists
In, in step (2), it is added except zirconium, hafnium, calcium agent quality be zirconium oxide in filtrate, hafnium oxide and calcium oxide quality sum 1~
2 times.
4. according to claim 1 or 2 remove zirconium, hafnium, the method for calcium from thick scandium oxide or scandium enriched substance, its feature exists
In in step (2), the temperature boiled is 100 DEG C, and the time boiled is 5~60min.
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| JP2005139047A (en) * | 2003-11-10 | 2005-06-02 | National Institute For Materials Science | Method for producing transparent scandium oxide sintered compact |
| CN102205986B (en) * | 2011-04-20 | 2013-04-17 | 湖南稀土金属材料研究院 | Method for separating zirconium from scandium-enriched raw material and method for preparing scandium oxide |
| CN102863004A (en) * | 2011-07-05 | 2013-01-09 | 北京有色金属研究总院 | Purification and preparation method of high-purity scandium oxide |
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