CN108220597A - The method of extracting and separating zirconium and hafnium in nitric acid medium - Google Patents
The method of extracting and separating zirconium and hafnium in nitric acid medium Download PDFInfo
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Abstract
The present invention provides a kind of method of extracting and separating zirconium and hafnium in nitric acid medium, belong to the fine separation technology field of substance, its synergistic extractant system being mainly made up of DIBK and phosphonic acids kind of extractants extracts the acid feed liquid of zirconium compounds, zirconium is made to enter water phase, hafnium enters organic phase and realizes separation, whole process does not need to, using noxious material, achieve the purpose that clean manufacturing.
Description
Technical field
The present invention relates to purification technique field, in particular to the method for extracting and separating zirconium in nitric acid medium and hafnium.
Background technology
The always symbiosis in nature of zirconium hafnium.Hafnium content (m in general commercially available zirconium chemicalsHf/m(Zr+Hf)) less (one
As be 1%~3%), if will have larger advantage using the extractant of preferential extraction hafnium when being detached to it.Because of " group of the lanthanides
Shrink ", atomic radius, the ionic radius of zirconium and hafnium are essentially identical, and physicochemical properties are closely similar, are separated from each other very tired
It is difficult, it is considered to be one of element of separation is most difficult in the periodic table of elements.But since zirconium and hafnium have different nuclearity energy, zirconium is to warm
Neutron absorption cross-section is small, is used as nuclear reactor involucrum and structural material extensively, and hafnium content is required to be less than 0.01% in nuclear grade zirconium,
And hafnium has big thermal neutron absorption cross section, is mainly used as the neutron control rod of nuclear reaction, zirconium content is required to be less than in core grade hafnium
2%.Therefore, separation of zirconium and hafnium is the key that obtain nuclear grade zirconium hafnium material.
Nuclear power is a kind of clean energy resource of economical and efficient, does not discharge sulfur dioxide, flue dust, nitrogen oxides and carbon dioxide.
Part thermoelectricity is substituted with nuclear power, can not only reduce exploitation, transport and the burning total amount of coal or power industry emission reduction pollution
The effective way of object even more slows down the important measures of global greenhouse effect.Each state is all greatly developing nuclear power in recent years, promotes
The development and concern of separation of zirconium and hafnium technology develop a variety of separation of zirconium and hafnium methods, such as fused salt rectification method, ion-exchange and solvent
Extraction etc..Since solvent extraction has, balancing speed is fast, good separating effect, treating capacity are big, operation is easily continuous, at low cost etc.
A series of outstanding advantages become the main method of separation of zirconium and hafnium, by extraction system point, there is neutral extraction system, acid extract body
System, alkaline extraction system, chelate extraction system and synergistic system.At present, the extractant and extraction system reported are only
MIBK, Cyanex 301, Cyanex 302 and D2EHPA isopreferences extract the hafnium that content is less in zirconium chemicals, equal in addition to MIBK
Be to weak solution (<10g/L zirconiums) it is extracted, it is unfavorable for industrial applications.
MIBK methods are the 20 th century America development and application seventies in industrial production, and the nuclear grade zirconium hafnium in the whole world nearly 2/3 produces use
The method separating zirconium and hafnium.MIBK methods are in SCN-The hafnium that content is less in zirconium hafnium is preferentially extracted under existence condition in hydrochloric acid medium, and is contained
It measures more zirconium and stays in water phase, so as to fulfill the separation (reaching 9 or so to the separation of zirconium hafnium) of zirconium and hafnium, extractant capacity
Greatly, it is efficient.But there are some shortcomings for MIBK methods：(1) solubility is up to 1.7wt% to MIBK in water (is that solubility is most in water
One of high extractant), solvent loss is big；(2) it needs to use unstable thiocyanic acid (and rhodanate), in acid condition
Toxic decomposition product is easily resolved into, such as hydrogen sulfide, methyl mercaptan and CN-Deng pollution environment；(3) MIBK has certain smell,
So that operation workshop condition is poor；4. MIBK flash-points are low, fire hazardous.For MIBK techniques there are the drawbacks of, show have very much
The necessity improved or replaced.
Diisobutyl ketone (DIBK) is a kind of neutrality oxygen-containing kind of extractants similar to MIBK structures, and the two has similar
Extraction ability and similar extraction mechanism, the difference in structure causes its property as extractant also variant, such as DIBK
47 DEG C of flash-point, and only 22.78 DEG C of the flash-point of MIBK；The water solubility of DIBK is 0.043wt%, and MIBK is up to 1.7wt%.Exactly
Due to these shortcomings of MIBK methods, its commercial Application is limited.
When using diisobutyl ketone (DIBK) as extractant at present, need using thiocyanic acid or its salt, due to thiocyanic acid
Or its salt has higher toxicity, in separation process not environmentally.
Invention content
The purpose of the present invention is to provide a kind of method of extracting and separating zirconium and hafnium in nitric acid medium, in separation process
In, without the use of noxious material, it can realize the clean manufacturing of separation of zirconium and hafnium process.
It is still another object of the present invention to provide a kind of methods of extracting and separating zirconium and hafnium in nitric acid medium, can be used for
The separation of zirconium and hafnium of zirconium compounds containing hafnium.
What the embodiment of the present invention was realized in：
The first aspect of the present invention：Extractant is mixed into extraction with the acid feed liquid that chemicals, the nitric acid by zirconium are mixed to form
It takes, gained raffinate mixes to obtain precipitated zirconium hydroxide with alkali after extracting split-phase, and the load organic phases containing hafnium are stripped with carbonate, instead
Extraction liquid mixed with alkali to obtain hafnium hydroxide precipitation, roast precipitated zirconium hydroxide and hafnium hydroxide precipitation, extractant include DIBK with
The mixture of phosphonic acids kind of extractants (key containing C-P) composition.
Preferably, phosphonic acids kind of extractants (key containing C-P) selected from by Cyanex921, Cyanex923, Cyanex925 and
At least one of group of Cyanex572 compositions.
Preferably, extractant carries out pre-extracted with nitric acid before extraction.
Preferably, concentration of nitric acid during pre-extracted for 2.0-6.0mol/L and/or, during pre-extracted, the extractant and nitre
Sour isometric progress.
Preferably, inorganic salts are further included in acid feed liquid.
The second aspect of the present invention：The chemicals of zirconium and nitric acid are mixed to form acid feed liquid, acid is extracted using extractant
Property feed liquid, extract split-phase after raffinate and the load organic phases containing hafnium, raffinate mixes to obtain precipitated zirconium hydroxide with alkali, containing hafnium
Load organic phases be stripped with carbonate, strip liquor mixes to obtain hafnium hydroxide precipitation with alkali, roasts precipitated zirconium hydroxide and hydrogen
Hafnium oxide precipitates, and extractant includes the mixture that DIBK and phosphonic acids kind of extractants (key containing C-P) form.
The advantageous effect of the embodiment of the present invention includes：The synergistic extractant system of DIBK and phosphonic acids kind of extractants (key containing C-P) composition
The relatively small hafnium of content in preferential extraction zirconium hafnium mixed solution, thus mass transfer is few, loading capacity is big；Technological process is simple, easy
Operation, extraction efficiency are high, and do not need in this separation process using such as thiocyanic acid or its salt high toxic material, entirely
Separation process is cleaned.
Specific embodiment
Purpose, technical scheme and advantage to make the embodiment of the present invention are clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, builds according to normal condition or manufacturer
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
The method of extracting and separating zirconium and hafnium in the nitric acid medium of the present invention is specifically described below.
The always symbiosis in nature of zirconium hafnium.Hafnium content (m in general commercially available zirconium chemicalsHf/m(Zr+Hf)) less (one
As be 1%~3%), if will have larger advantage using the extractant of preferential extraction hafnium when being detached to it.Because of " group of the lanthanides
Shrink ", atomic radius, the ionic radius of zirconium and hafnium are essentially identical, and physicochemical properties are closely similar, are separated from each other very tired
It is difficult, it is considered to be one of element of separation is most difficult in the periodic table of elements.But since zirconium and hafnium have different nuclearity energy, zirconium is to warm
Neutron absorption cross-section is small, is used as nuclear reactor involucrum and structural material extensively, and hafnium content is required to be less than 0.01% in nuclear grade zirconium,
And hafnium has big thermal neutron absorption cross section, is mainly used as the neutron control rod of nuclear reaction, zirconium content is required to be less than in core grade hafnium
2%.Therefore, separation of zirconium and hafnium is the key that obtain nuclear grade zirconium hafnium material.
As one aspect of the present invention, the present invention provides the side of extraction honey separating zirconium and hafnium in a kind of nitric acid medium
Method is mainly used for realizing efficiently separating for zirconium and hafnium, include the following steps：
There are many factor that separation of zirconium and hafnium is influenced in the system of Solvent Extraction Separation zirconium hafnium in the present invention, they are：
The volumn concentration of extractant；The concentration of zirconium hafnium in feed liquid, the concentration of sulfate, chlorine ion concentration, always free acidacidity and
Molar concentration of carbonate etc. during back extraction.In order to improve separating effect, in certain embodiments of the present invention, to obtained
Each constituent concentration in acid feed liquid is controlled, such as：
If the total concentration of zirconium ion and hafnium ion is less than 0.05mol/L in feed liquid, although being conducive to the separation of zirconium hafnium,
Feed liquid treating capacity is larger, and consumption total acid content is big.If the total concentration of zirconium ion and hafnium ion is higher than 2.0mol/L in feed liquid, when total
Free acidacidity is less than 0.05mol/L, and zirconium hafnium facile hydrolysis, relatively low to the extractibility of hafnium, separative efficiency is poor；When total free acidacidity
More than 4.0mol/L, separation of zirconium and hafnium coefficient reduces.In order to ensure the higher separating effect of zirconium hafnium, zirconium ion and hafnium ion in feed liquid
Total concentration be preferred in 0.05-2.0mol/L；Preferably 0.5-1.5mol/L, more preferably 1.0-1.5mol/L.
The always free acidacidity of feed liquid is 2.0-4.0mol/L, preferably 2.5-3.6mol/L.
It is preferred that in acid feed liquid, nitrate ion concentration is preferably controlled to 2.0-4.0mol/L, preferably
2.5-3.5mol/L optionally, may be incorporated into inorganic salts in acid feed liquid, when in acid feed liquid add in sulfate as nothing
During machine salt, may be incorporated into sulfate ion, sulfate ion concentration is preferably controlled to 0~1.0mol/L, such as sulfate radical from
Son a concentration of 0.2mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L and 0.8mol/L etc..
Optionally, acid feed liquid can also add in ammonium hydroxide etc. for adjusting the pH value in acid feed liquid.
Acid feed liquid obtained is extracted using extractant, wherein, extractant includes DIBK and phosphonic acids kind of extractants (contains C-
P keys) formed synergistic extractant system, phosphonic acids kind of extractants be selected from by Cyanex921, Cyanex923, Cyanex925 and Cyanex572
At least one of group of composition, you can with the synergistic extractant system that DIBK and Cyanex921 is used to be formed, can also use DIBK and
The synergistic extractant system that Cyanex923 is formed, the synergistic extractant system that DIBK and Cyanex925 can also be used to be formed, can also use
The synergistic extractant system that DIBK and Cyanex572 are formed, in certain embodiments of the present invention, can also use DIBK with
The synergistic extractant system that Cyanex921, Cyanex923, Cyanex925 and Cyanex572 are collectively formed, with using single extractant
Liquid-liquid extraction compare, synergic solvent extraction is more efficient.
Wherein, diisobutyl ketone (DIBK) is a kind of oxygen-containing kind of extractants of neutrality, and the flash-point of DIBK is 47 DEG C, and water solubility is
0.043wt%, it is water-soluble extremely low.
In certain embodiments of the present invention, it in extractant, is formed using DIBK and phosphonic acids kind of extractants (key containing C-P)
Synergistic extractant system when, the volume content of phosphonic acids kind of extractants (key containing C-P) is both preferably 2%~40%, more preferably 2%~
20%.It should be noted that in synergistic extractant system, can also use with Cyanex921 or Cyanex923 or Cyanex925 or
The similar extractant of Cyanex572 properties substitutes Cyanex921 or Cyanex923 or Cyanex925 or Cyanex572, also may be used
With further other extractants of addition with similar quality.
Phosphonic acids kind of extractants (key containing C-P) is a kind of organo-phosphine oxide kind of extractants, when other factors are fixed, with phosphonic acids
The increase of kind of extractants (key containing C-P) percent by volume, separation of zirconium and hafnium coefficient β value first increases to be reduced afterwards, if phosphonic acid extracts
Agent (key containing C-P) concentration of volume percent is too big to the extraction quantity of zirconium more than 40%, is unfavorable for the separation of zirconium hafnium, so it contains
It measures and is preferred for 2-20%.
During extraction, single-stage or multistage (such as 4~20 grades) may be used, and stream and/or inverse liquid mode carry out altogether, and two-phase is mixed
It is 2~30 minutes to close the time, and preferably 5~15 minutes, temperature was preferably controlled between 0~40 DEG C, such as 5 in the slot of extraction tank
DEG C, 10 DEG C, 15 DEG C, 20 DEG C, 25 DEG C, 30 DEG C and 35 DEG C etc..
The MIBK systems reported, DIBK-TBP systems, DIBK-P204 systems, DIBK-P350 systems, DIBK-TOPO bodies
It ties up to and uses SCN-Under conditions of show that the extraction mechanism of zirconium hafnium the composition of the extracted species of its zirconium is respectively：Zr(OH)2
(SCN)2·2MIBK、Zr(SCN)4·TBP·DIBK、Zr(SCN)3·HA2·DIBK、Zr(SCN)3.648·(HA2)0.3520·
(DIBK)0.0.1043With4、Zr4(OH)8(H2O)10SCN4Cl44S2B (wherein, B DIBK, S TOPO), the extracted species of hafnium
Composition is respectively：Hf(OH)2(SCN)2·2MIBK、Hf(SCN)4·TBP·DIBK、Hf(SCN)3·HA2·DIBK、Hf
(SCN)2.6843·(HA2)1.4157·(DIBK)0.689And Hf4(OH)8(H2O)8SCN84S4B illustrates SCN-Directly participate in extraction
Close the composition of object.Because of " lanthanide contract ", Hf4+Radius (71 × 10-12M) compare Zr4+Radius (72 × 10-12M) it is smaller.According to Louis
This hsab theory, Hf4+With Zr4+It is hard acid, but Hf4+Acidity is better than Zr4+Acidity is more easy to and hard base kind of extractants shape
Into relatively stable complex.The lewis base property of extractant is increasingly stronger in the following order：R2C=O<(RO)3P=O<R3P=O,
Illustrate that phosphonic acids kind of extractants (key containing C-P) is more easy to the Hf small with ionic radius than phosphoric acid kind of extractants (key containing C-O-P)4+Formed compared with
Stable extracted species, that is, it is easy to be extracted, so as to pass through DIBK and phosphonic acids kind of extractants (key containing C-P) composition association extraction body
System, can significantly improve its extraction yield to hafnium.
In certain embodiments of the present invention, extractant can be in advance with diluent mixed diluting, and diluent can select
From sulfonated kerosene, hexane, isooctane and 200# solvent naphthas etc., it should be understood that diluent can be by one kind or extremely of above-mentioned substance
Few two kinds of compositions.
Extractant is mixed with nitric acid and carries out pre-extracted, wherein, concentration of nitric acid is preferably 3.0-6.0mol/L, such as can be with
It is 2.0mol/L, 2.5mol/L, 3.0mol/L, 3.5mol/L, 4.0mol/L, 4.5mol/L, 5.0mol/L, 5.5mol/L,
6.0mol/L it waits.The effect of pre-extracted is that extractant is made to reach presaturation state.In pre-extracted, preferably extractant and nitric acid etc.
Volume carries out.
Extractant is extracted after carrying out pre-extracted as organic phase, acid feed liquid as water phase, mixing, extracts split-phase
Afterwards, zirconium is stayed in raffinate, is obtained no hafnium or is lacked the zirconium solution of hafnium, the hafnium in water phase enters organic phase, obtains the load containing hafnium
Organic phase.
To the obtained zirconium solution without hafnium, precipitated with alkali (such as ammonium hydroxide, caustic soda etc.), obtain precipitated zirconium hydroxide.
To the load organic phases containing hafnium, be stripped with carbonate, optionally, carbonate can be sodium carbonate, potassium carbonate,
Magnesium carbonate and aluminium carbonate etc., during back extraction, carbonate can be a kind of in above-mentioned substance or at least two mixture.Back extraction
Afterwards, hafnium enters water phase, and obtained strip liquor is rich hafnium solution.In obtained rich hafnium solution, mHf/m(Hf+Zr)Weight ratio be
10%~40%.Wherein, for example can be 0.05-5.0mol/L for the carbonate concentration of back extraction.
Then rich hafnium solution is precipitated with alkali (such as ammonium hydroxide, caustic soda etc.), obtains hafnium hydroxide precipitation.
Obtained precipitated zirconium hydroxide and hafnium hydroxide precipitation are washed with deionized water, the hydroxide after washing
Zirconium and hafnium hydroxide precipitation are roasted, it is preferable that and calcination temperature is 850-1800 DEG C, such as：Through 850 DEG C, 1000 DEG C, 1200
DEG C, 1400 DEG C, 1600 DEG C and 1800 DEG C roasted, when roasting, can also be carried out in a manner of gradient increased temperature.
Zirconium oxide is obtained after roasting as atomic energy level, the hafnium oxide containing zirconium also can reach atomic energy after further separation
Grade.
As another aspect of the present invention, the present invention provides a kind of method of extracting and separating zirconium and hafnium in nitric acid medium,
It is mainly used for realizing efficiently separating for zirconium and hafnium, roughly the same with above-mentioned separation method, difference lies in acid feed liquid is extracting
It prepares and obtains before taking：
First, acid feed liquid is made in the raw material to be separated containing zirconium and hafnium, i.e., mixed the chemicals of zirconium with nitric acid
Form acid feed liquid, it is preferable that inorganic salts can be added in acid feed liquid, inorganic salts can be selected from by ammonium chloride, sodium chloride, chlorine
Change at least one of group of magnesium, ammonium sulfate, sodium sulphate and magnesium sulfate composition.
In certain embodiments of the present invention, acid feed liquid can also add in a certain amount of ammonium hydroxide for adjusting in feed liquid
PH value.
Acid feed liquid can for example be produced by the following method：
First, zircon prepares zirconium chloride, zirconium chloride dissolving through carbonization, chlorination or the direct fluidizing chlorination of zircon
In water, it adds in ammonium hydroxide and inorganic salts is formulated as acid feed liquid, wherein ammonium hydroxide, inorganic salts can be quantitatively adding.
2nd, zircon adds in quantitative hydrochloric acid and inorganic salts is formulated as acid after alkali fusion, washing, dilute hydrochloric acid infusion solution
Property feed liquid.
3rd, zirconium oxychloride is directly dissolved in water, adds in quantitative hydrochloric acid and inorganic salts are formulated as acid feed liquid.
4th, zirconium oxide or metal zirconium or hafnium oxide or metal hafnium or zirconium waste material or the original of hafnium waste material containing other impurity
Material adds in quantitative nitric acid and inorganic salts is formulated as acid feed liquid by the first or second method preparation feed liquid.
In the acid feed liquid as made from above method, the composition of feed liquid is substantially as shown in table 1：
The composition of 1 acid feed liquid of table
The feature and performance of the present invention are described in further detail with reference to embodiments.
Embodiment 1
A kind of method of separating zirconium and hafnium, is as follows：
(1) acid feed liquid is prepared：Water phase is formed as initial Zr and Hf ions total concentration 1.5mol/L, wherein hafnium ion concentration about
For 0.018mol/L, aqueous phase acidity 2.87mol/L, (NH4)2SO4A concentration of 0.8mol/L.
(2) the mixing organic phase that extractant is formed using the Cyanex923 of the DIBK and 10% (v/v) of 90% (v/v), first
The nitric acid of extractant and isometric 5.5mol/L progress pre-extracted is primary, then using the extractant after pre-extracted as organic
Phase, for acid feed liquid as water phase, control is 2: 1 compared to (organic phase: water phase), carries out single-stage extraction to feed liquid at room temperature, two
The time is mixed as 10 minutes, zirconium is stayed in water phase, obtains the zirconium solution of few hafnium, then with ammonia precipitation process zirconium solution, obtains hydrogen-oxygen
Change zirconium precipitation, and the hafnium in water phase is extracted into organic phase entirely, obtains the load organic phases containing hafnium；
(3) load organic phases being stripped with 1.0mol/L potassium carbonate, back extraction is 1: 2 compared to (organic phase: water phase),
The two-phase mixtures time is 10 minutes, obtains the rich hafnium solution containing zirconium, is precipitated using ammonium hydroxide, obtains hafnium hydroxide precipitation；
(4) by zirconium hydroxide and hafnium hydroxide precipitation be washed with deionized respectively, the precipitated zirconium hydroxide after washing and
Hafnium hydroxide precipitation obtains the zirconium oxide of few hafnium and the hafnium oxide product containing zirconium through 1000 DEG C of roastings.
Before and after extraction in water phase zirconium hafnium metal ion total concentration EDTA titer titration measurings, acidity use hydrogen-oxygen
Change sodium titer titration measuring, the concentration of hafnium is measured, then calculate zirconium hafnium in organic phase respectively with minusing using ICP-MS methods
The total concentration of metal ion and the concentration of hafnium ion calculate distribution ratio, separation and extraction yield successively.
The concentration of metal ion in organic phase, zirconium hafnium distribution ratio, separation and extraction yield calculate as follows：
In formula：[Zr]o、[Hf]o--- the concentration of zirconium, hafnium, g/L respectively in organic phase；
[Zr]a、[Hf]a--- the concentration of zirconium, hafnium, g/L respectively in water phase；
--- the initial concentration of zirconium, hafnium ion, g/L respectively in water phase；
Va、Vo--- the respectively volume of water phase and organic phase, mL；
Dr(Zr)、Dr(Hf)--- it is respectively the distribution ratio of zirconium, hafnium；
[Zr]ea、[Hf]ea--- respectively balance when water phase in zirconium, hafnium ion concentration, g/L；
[Zr]eo、[Hf]eo--- respectively balance when organic phase in zirconium, hafnium ion concentration, g/L；
β --- it is the separation of zirconium hafnium；
EZr、EHf--- it is respectively extraction yield of the organic phase to zirconium, hafnium.
By calculating, in the present embodiment, the extraction yield to hafnium is 87.77%, and the extraction yield of zirconium is 15.99%, zirconium hafnium
Separation reach 37.
Embodiment 2
Organic phase composition is the DIBK of 90% (v/v), the isooctane of the Cyanex921 and 8% (v/v) of 2% (v/v) (are made
For diluent), and it is primary with the nitric acid pre-extracted of isometric 6.0mol/L in advance, and water phase composition is initial Zr and Hf ions total concentration
A concentration of 0.018mol/L of 1.5mol/L, wherein hafnium ion, aqueous phase acidity 3.0mol/L, (NH4)2SO4Addition is
1.0mol/L, control are comparably 2: 1, carry out single-stage extraction at room temperature, and the two-phase mixtures time is 5 minutes, is extracted after split-phase
Extraction raffinate and the load organic phases containing hafnium, raffinate with ammonia precipitation process, obtain precipitated zirconium hydroxide again；Load organic phases are used
1.0mol/L potassium carbonate is stripped, and it is 1: 2 to wash with comparing for back extraction, and the two-phase mixtures time is 5 minutes, is obtained containing zirconium
Rich hafnium solution, is precipitated using ammonium hydroxide, obtains the hafnium hydroxide precipitation containing zirconium.Other operating procedures are the same as embodiment 1.
By calculating, in the present embodiment, the extraction yield to hafnium is 66.52%, and the extraction yield of zirconium is 11.53%, zirconium hafnium
Separation reaches 10.
Embodiment 3
Organic phase composition is the DIBK of 90% (v/v), the sulfonated kerosene of the Cyanex923 and 2% (v/v) of 8% (v/v)
(as diluent), and it is primary with the nitric acid pre-extracted of isometric 6.0mol/L in advance, and water phase composition is total for initial Zr and Hf ions
A concentration of 0.018mol/L of concentration 1.5mol/L, wherein hafnium ion, aqueous phase acidity 3.0mol/L, (NH4)2SO4Addition is
0.8mol/L, control are comparably 2: 1, carry out single-stage extraction at room temperature, and the two-phase mixtures time is 5 minutes, is extracted after split-phase
Extraction raffinate and the load organic phases containing hafnium, raffinate with ammonia precipitation process, obtain the precipitated zirconium hydroxide of few hafnium again；By load organic phases
It is stripped with 1.0mol/L sodium carbonate, it is 1: 2 to wash with comparing for back extraction, and the two-phase mixtures time is 5 minutes, is obtained containing zirconium
Rich hafnium solution, precipitated using ammonium hydroxide, obtain containing zirconium hafnium hydroxide precipitation.Other operating procedures are the same as embodiment 1.
By calculating, in the present embodiment, the extraction yield to hafnium is 84.98%, and the extraction yield of zirconium is 16.51%, zirconium hafnium
Separation reaches 20.
Embodiment 4
Organic phase composition is the Cyanex925 of the DIBK and 40% (v/v) of 60% (v/v), and in advance with isometric
The nitric acid pre-extracted of 4.0mol/L is primary, and water phase composition is initial Zr and Hf ions total concentration 0.05mol/L, wherein hafnium ion concentration
For 0.0006mol/L, aqueous phase acidity 2.0mol/L, (NH4)2SO4Addition is 0.2mol/L, and control is comparably 2: 1, in room
Temperature is lower to carry out single-stage extraction, and the two-phase mixtures time is 2 minutes, obtains raffinate and the load organic phases containing hafnium after split-phase, raffinate
Liquid with sodium hydroxide pellets, obtains the precipitated zirconium hydroxide of few hafnium again；Load organic phases are carried out instead with 3.0mol/L potassium carbonate
Extraction, it is 1: 2 to wash with comparing for back extraction, and the two-phase mixtures time is 5 minutes, obtains the rich hafnium solution containing zirconium, wherein, rich hafnium is molten
In liquid, mHf/m(Hf+Zr)Weight ratio be 18%.It is precipitated using ammonium hydroxide, obtains the hafnium hydroxide precipitation containing zirconium.Other operations
Step is the same as embodiment 1.
By calculating, in the present embodiment, the extraction yield to hafnium is 72.06%, and the extraction yield of zirconium is 16.29%, zirconium hafnium
Separation reaches 13.
Embodiment 5
Organic phase composition is the Cyanex923 of the DIBK and 20% (v/v) of 80% (v/v), and in advance with isometric
The nitric acid pre-extracted of 3.0mol/L is primary, and water phase composition is initial Zr and Hf ions total concentration 1.5mol/L, wherein hafnium ion concentration
For 0.018mol/L, aqueous phase acidity 1.5mol/L, NH4Cl additions are 1.25mol/L, and control is comparably 2: 1, at room temperature
Single-stage extraction is carried out, the two-phase mixtures time is 30 minutes, raffinate and the load organic phases containing hafnium is obtained after split-phase, raffinate is again
With ammonia precipitation process, the precipitated zirconium hydroxide of few hafnium is obtained；Load organic phases are stripped with 2.0mol/L magnesium carbonate, washing and
Comparing for back extraction is 1: 2, and the two-phase mixtures time is 5 minutes, obtains the rich hafnium solution containing zirconium, wherein, in rich hafnium solution, mHf/
m(Hf+Zr)Weight ratio be 10%.It is precipitated using ammonium hydroxide, obtains the hafnium hydroxide precipitation containing zirconium.Other operating procedures are the same as real
Apply example 1.
By calculating, in the present embodiment, the extraction yield to hafnium is 35.74%, and the extraction yield of zirconium is 17.25%, zirconium hafnium
Separation reaches 6.
Embodiment 6
Organic phase composition is the Cyanex923 of the DIBK and 30% (v/v) of 70% (v/v), and in advance with isometric
The nitric acid pre-extracted of 5.0mol/L is primary, and water phase composition is initial Zr and Hf ions total concentration 2.0mol/L, wherein hafnium ion concentration
For 0.024mol/L, aqueous phase acidity 2.5mol/L, MgCl2Addition is 1.0mol/L, and control is comparably 2: 1, at room temperature
Single-stage extraction is carried out, the two-phase mixtures time is 25 minutes, raffinate and the load organic phases containing hafnium is obtained after split-phase, raffinate is again
It is precipitated with potassium hydroxide, obtains the precipitated zirconium hydroxide of few hafnium；Load organic phases with 2.0mol/L aluminium carbonates are stripped, are washed
It is 1: 2 to wash with comparing for back extraction, and the two-phase mixtures time is 25 minutes, obtains the rich hafnium solution containing zirconium, wherein, rich hafnium solution
In, mHf/m(Hf+Zr)Weight ratio be 30%.It is precipitated using ammonium hydroxide, obtains the hafnium hydroxide precipitation containing zirconium.Other operation steps
Suddenly with embodiment 1.
By calculating, in the present embodiment, the extraction yield to hafnium is 79.72%, and the extraction yield of zirconium is 17.02%, zirconium hafnium
Separation reaches 18.
Embodiment 7
Organic phase composition is the Cyanex923 of the DIBK and 5% (v/v) of 95% (v/v), and in advance with isometric
The nitric acid pre-extracted of 6.0mol/L is primary, and water phase composition is initial Zr and Hf ions total concentration 0.5mol/L, wherein hafnium ion concentration
For 0.006mol/L, aqueous phase acidity 3.0mol/L, (NH4)2SO4Addition is 0.8mol/L, and control is comparably 2: 1, in room temperature
Lower carry out single-stage extraction, two-phase mixtures time are 10 minutes, and raffinate and the load organic phases containing hafnium, raffinate are obtained after split-phase
Again with ammonia precipitation process, the precipitated zirconium hydroxide of few hafnium is obtained；Load organic phases with 3.0mol/L sodium carbonate are stripped, are washed
It is 1: 2 with comparing for back extraction, the two-phase mixtures time is 10 minutes, obtains the rich hafnium solution containing zirconium, wherein, in rich hafnium solution,
mHf/m(Hf+Zr)Weight ratio be 10%.It is precipitated using ammonium hydroxide, obtains the hafnium hydroxide precipitation containing zirconium.Other operating procedures
With embodiment 1.
By calculating, in the present embodiment, the extraction yield to hafnium is 66.52%, and the extraction yield of zirconium is 21.46%, zirconium hafnium
Separation reaches 6.
Embodiment 8
Organic phase composition is the Cyanex923 of the DIBK and 35% (v/v) of 65% (v/v), and in advance with isometric
The nitric acid pre-extracted of 6.0mol/L is primary, and water phase composition is initial Zr and Hf ions total concentration 1.5mol/L, wherein hafnium ion concentration
For 0.018mol/L, aqueous phase acidity 3.0mol/L, (NH4)2SO4Addition is 0.8mol/L, and control is comparably 2: 1, in room temperature
Lower carry out single-stage extraction, two-phase mixtures time are 15 minutes, then with ammonia precipitation process, obtain the precipitated zirconium hydroxide of few hafnium；It will be negative
It carries organic phase to be stripped with 1.0mol/L sodium carbonate, it is 1: 2 to wash with comparing for back extraction, and the two-phase mixtures time is 15 points
Clock obtains the rich hafnium solution containing zirconium, wherein, in rich hafnium solution, mHf/m(Hf+Zr)Weight ratio be 40%.It is sunk using ammonium hydroxide
It forms sediment, obtains the hafnium hydroxide precipitation containing zirconium.Other operating procedures are the same as embodiment 1.
By calculating, in the present embodiment, the extraction yield to hafnium is 86.08%, and the extraction yield of zirconium is 16.05%, zirconium hafnium
Separation reaches 34.
Embodiment 9
Organic phase composition is the hexane of the Cyanex923 and 8% (v/v) of the DIBK and 2% (v/v) of 90% (v/v), and
Primary with the nitric acid pre-extracted of isometric 2.0mol/L in advance, water phase composition is initial Zr and Hf ions total concentration 1.0mol/L,
Middle a concentration of 0.012mol/L of hafnium ion, aqueous phase acidity 1.0mol/L, (NH4)2SO4Addition is 0.6mol/L, and control is compared
It is 2: 1, carries out single-stage extraction at room temperature, the two-phase mixtures time is 5 minutes, and raffinate and the load containing hafnium are obtained after split-phase to be had
Machine phase, raffinate with ammonia precipitation process, obtain the precipitated zirconium hydroxide of few hafnium again；By load organic phases with 2.5mol/L sodium carbonate into
Row back extraction, it is 1: 2 to wash with comparing for back extraction, and the two-phase mixtures time is 5 minutes, the rich hafnium solution containing zirconium is obtained, using ammonia
Water is precipitated, and obtains the hafnium hydroxide precipitation containing zirconium.Other operating procedures are the same as embodiment 1.
By calculating, in the present embodiment, the extraction yield to hafnium is 49.80%, and the extraction yield of zirconium is 13.68%, zirconium hafnium
Separation reaches 6.
Embodiment 10
Organic phase composition is the isooctane of the Cyanex923 and 2% (v/v) of the DIBK and 8% (v/v) of 90% (v/v),
And it is primary with the nitric acid pre-extracted of isometric 5.0mol/L in advance, water phase composition is initial Zr and Hf ions total concentration 2.0mol/L,
Wherein a concentration of 0.024mol/L of hafnium ion, aqueous phase acidity 2.5mol/L, (NH4)2SO4Addition is 1.0mol/L, controls phase
Than being 2: 1, single-stage extraction is carried out at room temperature, the two-phase mixtures time is 10 minutes, and raffinate and bearing containing hafnium are obtained after split-phase
Organic phase is carried, raffinate with ammonia precipitation process, obtains the precipitated zirconium hydroxide of few hafnium again；By load organic phases 1.5mol/L carbonic acid
Sodium is stripped, and it is 1: 2 to wash with comparing for back extraction, and the two-phase mixtures time is 10 minutes, obtains the rich hafnium solution containing zirconium, adopts
It is precipitated with ammonium hydroxide, obtains the hafnium hydroxide precipitation containing zirconium.Other operating procedures are the same as embodiment 1.
By calculating, in the present embodiment, the extraction yield to hafnium is 72.15%, and the extraction yield of zirconium is 16.66%, zirconium hafnium
Separation reaches 12.
Embodiment 11
Organic phase composition is the Cyanex572 of the DIBK of 90% (v/v), 10% (v/v), and in advance with isometric
The nitric acid pre-extracted of 4.0mol/L is primary, and water phase composition is initial Zr and Hf ions total concentration 1.5mol/L, wherein hafnium ion concentration
For 0.018mol/L, aqueous phase acidity 2.0mol/L, (NH4)2SO4Addition is 0.8mol/L, and control is comparably 2: 1, in room temperature
Lower carry out single-stage extraction, two-phase mixtures time are 10 minutes, and raffinate and the load organic phases containing hafnium, raffinate are obtained after split-phase
Again with ammonia precipitation process, precipitated zirconium hydroxide is obtained；Load organic phases with 1.0mol/L potassium carbonate are stripped, washs and is stripped
Compared to being 1: 2, the two-phase mixtures time is 10 minutes, obtains the rich hafnium solution containing zirconium, is precipitated, contained using ammonium hydroxide
The hafnium hydroxide precipitation of zirconium.Other operating procedures are the same as embodiment 1.
By calculating, in the present embodiment, the extraction yield to hafnium is 66.96%, and the extraction yield of zirconium is 8.68%, point of zirconium hafnium
Reach 26 from coefficient.
Embodiment 12
Organic phase composition is the DIBK of 90% (v/v), the sulfonated kerosene of the Cyanex572 and 8% (v/v) of 2% (v/v)
(as diluent), and it is primary with the nitric acid pre-extracted of isometric 4.0mol/L in advance, and water phase composition is total for initial Zr and Hf ions
A concentration of 0.018mol/L of concentration 1.5mol/L, wherein hafnium ion, aqueous phase acidity 2.0mol/L, (NH4)2SO4Addition is
0.6mol/L, control are comparably 2: 1, carry out single-stage extraction at room temperature, and the two-phase mixtures time is 5 minutes, is extracted after split-phase
Extraction raffinate and the load organic phases containing hafnium, raffinate with ammonia precipitation process, obtain precipitated zirconium hydroxide again；Load organic phases are used
1.0mol/L potassium carbonate is stripped, and it is 1: 2 to wash with comparing for back extraction, and the two-phase mixtures time is 5 minutes, is obtained containing zirconium
Rich hafnium solution, is precipitated using ammonium hydroxide, obtains the hafnium hydroxide precipitation containing zirconium.Other operating procedures are the same as embodiment 1.
By calculating, in the present embodiment, the extraction yield to hafnium is 60.44%, and the extraction yield of zirconium is 8.62%, point of zirconium hafnium
Reach 10 from coefficient.
Embodiment 13
Organic phase composition is the DIBK of 90% (v/v), the Cyanex925 of the Cyanex923 and 2% (v/v) of 8% (v/v),
And it is primary with the nitric acid pre-extracted of isometric 6.0mol/L in advance, water phase composition is initial Zr and Hf ions total concentration 1.5mol/L,
Wherein a concentration of 0.018mol/L of hafnium ion, aqueous phase acidity 3.0mol/L, (NH4)2SO4Addition is 0.8mol/L, controls phase
Than being 2: 1, single-stage extraction is carried out at room temperature, the two-phase mixtures time is 5 minutes, and raffinate and the load containing hafnium are obtained after split-phase
Organic phase, raffinate with ammonia precipitation process, obtain the precipitated zirconium hydroxide of few hafnium again；By load organic phases 1.0mol/L sodium carbonate
It is stripped, it is 1: 2 to wash with comparing for back extraction, and the two-phase mixtures time is 5 minutes, obtains the rich hafnium solution containing zirconium, is used
Ammonium hydroxide is precipitated, and obtains the hafnium hydroxide precipitation containing zirconium.Other operating procedures are the same as embodiment 1.
By calculating, in the present embodiment, the extraction yield to hafnium is 84.46%, and the extraction yield of zirconium is 15.71%, zirconium hafnium
Separation reaches 30.
Embodiment 14
Organic phase composition is the Cyanex572 of the DIBK and 40% (v/v) of 60% (v/v), and in advance with isometric
The nitric acid pre-extracted of 4.0mol/L is primary, and water phase composition is initial Zr and Hf ions total concentration 1.0mol/L, wherein hafnium ion concentration
For 0.012mol/L, aqueous phase acidity 2.0mol/L, (NH4)2SO4Addition is 1.25mol/L, and control is comparably 2: 1, in room
Temperature is lower to carry out single-stage extraction, and the two-phase mixtures time is 2 minutes, obtains raffinate and the load organic phases containing hafnium after split-phase, raffinate
Liquid with sodium hydroxide pellets, obtains the precipitated zirconium hydroxide of few hafnium again；Load organic phases are carried out instead with 2.0mol/L potassium carbonate
Extraction, it is 1: 2 to wash with comparing for back extraction, and the two-phase mixtures time is 5 minutes, obtains the rich hafnium solution containing zirconium, wherein, rich hafnium is molten
In liquid, mHf/m(Hf+Zr)Weight ratio be 30%.It is precipitated using ammonium hydroxide, obtains the hafnium hydroxide precipitation containing zirconium.Other operations
Step is the same as embodiment 1.
By calculating, in the present embodiment, the extraction yield to hafnium is 66.06%, and the extraction yield of zirconium is 9.26%, point of zirconium hafnium
Reach 20 from coefficient.
Embodiment 15
Organic phase composition is the Cyanex921 of the DIBK and 20% (v/v) of 80% (v/v), and in advance with isometric
The nitric acid pre-extracted of 3.0mol/L is primary, and water phase composition is initial Zr and Hf ions total concentration 2.0mol/L, wherein hafnium ion concentration
For 0.024mol/L, aqueous phase acidity 1.5mol/L, NH4Cl additions are 1.0mol/L, and control is comparably 2: 1, at room temperature
Single-stage extraction is carried out, the two-phase mixtures time is 30 minutes, raffinate and the load organic phases containing hafnium is obtained after split-phase, raffinate is again
With ammonia precipitation process, the precipitated zirconium hydroxide of few hafnium is obtained；Load organic phases are stripped with 1.0mol/L magnesium carbonate, washing and
Comparing for back extraction is 1: 2, and the two-phase mixtures time is 5 minutes, obtains the rich hafnium solution containing zirconium, wherein, in rich hafnium solution, mHf/
m(Hf+Zr)Weight ratio be 10%.It is precipitated using ammonium hydroxide, obtains the hafnium hydroxide precipitation containing zirconium.Other operating procedures are the same as real
Apply example 1.
By calculating, in the present embodiment, the extraction yield to hafnium is 35.52%, and the extraction yield of zirconium is 17.20%, zirconium hafnium
Separation reaches 6.
Embodiment 16
Organic phase composition is the Cyanex925 of the DIBK and 30% (v/v) of 70% (v/v), and in advance with isometric
The nitric acid pre-extracted of 5.0mol/L is primary, and water phase composition is initial Zr and Hf ions total concentration 2.0mol/L, wherein hafnium ion concentration
For 0.024mol/L, aqueous phase acidity 2.5mol/L, MgCl2Addition is 0.6mol/L, and control is comparably 2: 1, at room temperature
Single-stage extraction is carried out, the two-phase mixtures time is 25 minutes, raffinate and the load organic phases containing hafnium is obtained after split-phase, raffinate is again
It is precipitated with potassium hydroxide, obtains the precipitated zirconium hydroxide of few hafnium；Load organic phases with 1.0mol/L aluminium carbonates are stripped, are washed
It is 1: 2 to wash with comparing for back extraction, and the two-phase mixtures time is 25 minutes, obtains the rich hafnium solution containing zirconium, wherein, rich hafnium solution
In, mHf/m(Hf+Zr)Weight ratio be 25%.It is precipitated using ammonium hydroxide, obtains the hafnium hydroxide precipitation containing zirconium.Other operation steps
Suddenly with embodiment 1.
By calculating, in the present embodiment, the extraction yield to hafnium is 70.16%, and the extraction yield of zirconium is 16.66%, zirconium hafnium
Separation reaches 15.
Embodiment 17
Organic phase composition is the Cyanex572 of the DIBK and 5% (v/v) of 95% (v/v), and in advance with isometric
The nitric acid pre-extracted of 3.0mol/L is primary, and water phase composition is initial Zr and Hf ions total concentration 0.5mol/L, wherein hafnium ion concentration
For 0.006mol/L, aqueous phase acidity 1.5mol/L, (NH4)2SO4Addition is 0.8mol/L, and control is comparably 2: 1, in room temperature
Lower carry out single-stage extraction, two-phase mixtures time are 10 minutes, and raffinate and the load organic phases containing hafnium, raffinate are obtained after split-phase
Again with ammonia precipitation process, the precipitated zirconium hydroxide of few hafnium is obtained；Load organic phases with 2.0mol/L sodium carbonate are stripped, are washed
It is 1: 2 with comparing for back extraction, the two-phase mixtures time is 10 minutes, obtains the rich hafnium solution containing zirconium, wherein, in rich hafnium solution,
mHf/m(Hf+Zr)Weight ratio be 20%.It is precipitated using ammonium hydroxide, obtains the hafnium hydroxide precipitation containing zirconium.Other operating procedures
With embodiment 1.
By calculating, in the present embodiment, the extraction yield to hafnium is 56.42%, and the extraction yield of zirconium is 8.28%, point of zirconium hafnium
Reach 10 from coefficient.
Embodiment 18
Organic phase composition is the Cyanex572 of the DIBK and 35% (v/v) of 65% (v/v), and in advance with isometric
The nitric acid pre-extracted of 4.4mol/L is primary, and water phase composition is initial Zr and Hf ions total concentration 1.0mol/L, wherein hafnium ion concentration
For 0.012mol/L, aqueous phase acidity 2.2mol/L, (NH4)2SO4Addition is 0.8mol/L, and control is comparably 2: 1, in room temperature
Lower carry out single-stage extraction, two-phase mixtures time are 15 minutes, then with ammonia precipitation process, obtain the precipitated zirconium hydroxide of few hafnium；It will be negative
It carries organic phase to be stripped with 1.0mol/L sodium carbonate, it is 1: 2 to wash with comparing for back extraction, and the two-phase mixtures time is 15 points
Clock obtains the rich hafnium solution containing zirconium, wherein, in rich hafnium solution, mHf/m(Hf+Zr)Weight ratio be 30%.It is sunk using ammonium hydroxide
It forms sediment, obtains the hafnium hydroxide precipitation containing zirconium.Other operating procedures are the same as embodiment 1.
By calculating, in the present embodiment, the extraction yield to hafnium is 70.84%, and the extraction yield of zirconium is 9.04%, point of zirconium hafnium
Reach 22 from coefficient.
Embodiment 19
Organic phase composition is the hexane of the Cyanex921 and 8% (v/v) of the DIBK and 2% (v/v) of 90% (v/v), and
Primary with the nitric acid pre-extracted of isometric 2.0mol/L in advance, water phase composition is initial Zr and Hf ions total concentration 2.0mol/L,
Middle a concentration of 0.024mol/L of hafnium ion, aqueous phase acidity 1.0mol/L, (NH4)2SO4Addition is 0.8mol/L, and control is compared
It is 2: 1, carries out single-stage extraction at room temperature, the two-phase mixtures time is 5 minutes, and raffinate and the load containing hafnium are obtained after split-phase to be had
Machine phase, raffinate with ammonia precipitation process, obtain the precipitated zirconium hydroxide of few hafnium again；By load organic phases with 2.0mol/L sodium carbonate into
Row back extraction, it is 1: 2 to wash with comparing for back extraction, and the two-phase mixtures time is 5 minutes, the rich hafnium solution containing zirconium is obtained, using ammonia
Water is precipitated, and obtains the hafnium hydroxide precipitation containing zirconium.Other operating procedures are the same as embodiment 1.
By calculating, in the present embodiment, the extraction yield to hafnium is 49.45%, and the extraction yield of zirconium is 13.24%, zirconium hafnium
Separation reaches 7.
Embodiment 20
Organic phase composition is the isooctane of the Cyanex572 and 2% (v/v) of the DIBK and 8% (v/v) of 90% (v/v),
And it is primary with the nitric acid pre-extracted of isometric 4.0mol/L in advance, water phase composition is initial Zr and Hf ions total concentration 2.0mol/L,
Wherein a concentration of 0.024mol/L of hafnium ion, aqueous phase acidity 2.0mol/L, (NH4)2SO4Addition is 0.8mol/L, controls phase
Than being 2: 1, single-stage extraction is carried out at room temperature, the two-phase mixtures time is 10 minutes, and raffinate and bearing containing hafnium are obtained after split-phase
Organic phase is carried, raffinate with ammonia precipitation process, obtains the precipitated zirconium hydroxide of few hafnium again；By load organic phases 1.0mol/L carbonic acid
Sodium is stripped, and it is 1: 2 to wash with comparing for back extraction, and the two-phase mixtures time is 10 minutes, obtains the rich hafnium solution containing zirconium, adopts
It is precipitated with ammonium hydroxide, obtains the hafnium hydroxide precipitation containing zirconium.Other operating procedures are the same as embodiment 1.
By calculating, in the present embodiment, the extraction yield to hafnium is 64.22%, and the extraction yield of zirconium is 8.56%, point of zirconium hafnium
Reach 15 from coefficient.
Embodiment 21
Difference lies in the synergistic extractant system of selection is different, and in the present embodiment, the association of selection extracts with embodiment 1 for the present embodiment
System is matched using the DIBK of 90% (v/v), the Cyanex572 of the Cyanex923 and 5% (v/v) of 5% (v/v), other raw materials
Than all sames such as, preparation methods.
Embodiments described above is part of the embodiment of the present invention, instead of all the embodiments.The reality of the present invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of the selected implementation of the present invention
Example.Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without making creative work
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of method of extracting and separating zirconium and hafnium in nitric acid medium, which is characterized in that include the following steps；
By extractant and the acid feed liquid hybrid extraction being mixed to form by chemicals, the nitric acid of zirconium, gained raffinate after split-phase is extracted
Liquid mixes to obtain precipitated zirconium hydroxide with alkali, and the load organic phases containing hafnium are stripped with carbonate, and strip liquor mixes to obtain hydroxide with alkali
Hafnium precipitates, and roasts the precipitated zirconium hydroxide and hafnium hydroxide precipitation, the extractant includes DIBK and phosphonic acid extracts
The mixture that agent is taken to form；
Preferably, phosphonic acids kind of extractants is selected from the group being made of Cyanex921, Cyanex923, Cyanex925 and Cyanex572
At least one of；
Preferably, extractant carries out pre-extracted with nitric acid before extraction；
Preferably, concentration of nitric acid during pre-extracted for 2.0-6.0mol/L and/or, during pre-extracted, the extractant and nitric acid etc.
Volume carries out；
Preferably, inorganic salts are further included in acid feed liquid.
2. the method for extracting and separating zirconium and hafnium in nitric acid medium according to claim 1, which is characterized in that the acid material
In liquid, always free acidacidity is 2.0-4.0mol/L, preferably 2.5-3.6mol/L；
And/or in the acid feed liquid, the total concentration of zirconium ion and hafnium ion is 0.05-2.0mol/L, preferably 0.5-
1.5mol/L, more preferably 1.0-1.5mol/L.
3. the method for extracting and separating zirconium and hafnium in nitric acid medium according to claim 2, which is characterized in that the acid material
In liquid, a concentration of 2.0-4.0mol/L of nitrate ion, preferably 2.5-3.5mol/L；
And/or a concentration of 0-1.0mol/L of sulfate ion.
4. the method for extracting and separating zirconium and hafnium in nitric acid medium according to claim 1, which is characterized in that the inorganic salts
Selected from least one of group being made of ammonium chloride, sodium chloride, magnesium chloride, ammonium sulfate and sodium sulphate.
5. the method for extracting and separating zirconium and hafnium in nitric acid medium according to claim 1, which is characterized in that the extractant
In, the volume fraction of phosphonic acids kind of extractants is 2vt%-40vt%, preferably 2vt%-20vt%；
And/or in the strip liquor, mHf/m(Hf+Zr)Weight ratio be 10%~40%.
6. the method for extracting and separating zirconium and hafnium in nitric acid medium according to claim 5, which is characterized in that, will before extraction
The extractant is mixed with diluent, it is preferable that the diluent is selected from by sulfonated kerosene, hexane, isooctane and 200# solvents
At least one of group of oil composition.
7. according to the method for extracting and separating zirconium and hafnium in claim 1-6 any one of them nitric acid mediums, which is characterized in that extraction
It takes and is carried out using single-stage or multistage stream altogether and/or inverse liquid mode, it is preferable that the two-phase mixtures time is 2-30min, more preferably 5-
15min；Preferably, temperature is 0-40 DEG C in the slot of extraction tank during extraction.
8. according to the method for extracting and separating zirconium and hafnium in claim 1-6 any one of them nitric acid mediums, the carbonate choosing
At least one of the group that free sodium carbonate, potassium carbonate, magnesium carbonate and aluminium carbonate form.
9. according to the method for extracting and separating zirconium and hafnium in claim 1-6 any one of them nitric acid mediums, which is characterized in that roasting
Burning carried out under the conditions of 850-1800 DEG C and/or, before roasting, the precipitated zirconium hydroxide and the hafnium hydroxide are precipitated into
Row washing.
10. a kind of method of extracting and separating zirconium and hafnium in nitric acid medium, which is characterized in that the chemicals of zirconium is mixed into shape with nitric acid
Into acid feed liquid,
Extract the acid feed liquid using extractant, extract after split-phase to obtain raffinate and the load organic phases containing hafnium, raffinate with
Alkali mixes to obtain precipitated zirconium hydroxide, and the load organic phases containing hafnium are stripped with carbonate, strip liquor mixed with alkali hafnium hydroxide sinks
It forms sediment, roasts the precipitated zirconium hydroxide and hafnium hydroxide precipitation, the extractant include DIBK and phosphonic acids kind of extractants
The mixture of composition.
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| CN201810005244.7A CN108220597A (en) | 2018-01-03 | 2018-01-03 | The method of extracting and separating zirconium and hafnium in nitric acid medium |
| PCT/CN2018/072340 WO2019134185A1 (en) | 2018-01-03 | 2018-01-12 | Method for extracting and separating zirconium and hafnium from nitric acid medium |
| US16/204,126 US20200024687A1 (en) | 2018-01-03 | 2018-11-29 | Method for extracting and separating zirconium and hafnium in nitric acid medium |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110746454A (en) * | 2019-11-12 | 2020-02-04 | 济南大学 | Dual-phosphoric acid extracting agent for extracting and separating zirconium and hafnium and preparation method thereof |
| CN111041241A (en) * | 2019-12-10 | 2020-04-21 | 中核二七二铀业有限责任公司 | Preparation method of nuclear grade pure zirconium nitrate |
| CN112573571A (en) * | 2020-11-20 | 2021-03-30 | 中核二七二铀业有限责任公司 | Method for preparing hafnium dioxide from sodium hafnocenate |
| CN113916870A (en) * | 2021-10-20 | 2022-01-11 | 中国核动力研究设计院 | Separation and determination method for impurity elements in high-purity zirconium and hafnium |
| CN114317959A (en) * | 2021-12-31 | 2022-04-12 | 中核二七二铀业有限责任公司 | Method for recovering zirconium and hafnium from zirconium and hafnium separation raffinate water precipitation filter residue |
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| CN110747357B (en) * | 2019-11-12 | 2021-06-25 | 济南大学 | Method for extracting and separating zirconium and hafnium by using biphosphoric acid extracting agent |
| CN112694124A (en) * | 2020-11-20 | 2021-04-23 | 中核二七二铀业有限责任公司 | Method for preparing high-purity hafnium dioxide |
| CN112591758B (en) * | 2021-01-08 | 2022-10-28 | 景德镇皓旭陶瓷原料有限公司 | Method for efficiently recycling zirconium and silicon in zirconium slag |
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| CN110746454A (en) * | 2019-11-12 | 2020-02-04 | 济南大学 | Dual-phosphoric acid extracting agent for extracting and separating zirconium and hafnium and preparation method thereof |
| CN110746454B (en) * | 2019-11-12 | 2021-07-13 | 济南大学 | Dual-phosphoric acid extracting agent for extracting and separating zirconium and hafnium and preparation method thereof |
| CN111041241A (en) * | 2019-12-10 | 2020-04-21 | 中核二七二铀业有限责任公司 | Preparation method of nuclear grade pure zirconium nitrate |
| CN112573571A (en) * | 2020-11-20 | 2021-03-30 | 中核二七二铀业有限责任公司 | Method for preparing hafnium dioxide from sodium hafnocenate |
| CN113916870A (en) * | 2021-10-20 | 2022-01-11 | 中国核动力研究设计院 | Separation and determination method for impurity elements in high-purity zirconium and hafnium |
| CN113916870B (en) * | 2021-10-20 | 2024-01-23 | 中国核动力研究设计院 | Separation and determination method for impurity elements in high-purity zirconium and hafnium |
| CN114317959A (en) * | 2021-12-31 | 2022-04-12 | 中核二七二铀业有限责任公司 | Method for recovering zirconium and hafnium from zirconium and hafnium separation raffinate water precipitation filter residue |
| CN114317959B (en) * | 2021-12-31 | 2024-01-12 | 中核二七二铀业有限责任公司 | Method for recovering zirconium and hafnium from residue water precipitation filter residues of zirconium and hafnium separation |
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| US20200024687A1 (en) | 2020-01-23 |
| WO2019134185A1 (en) | 2019-07-11 |
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