WO2019134184A1 - 盐酸介质中萃取分离锆和铪的方法 - Google Patents

盐酸介质中萃取分离锆和铪的方法 Download PDF

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Publication number
WO2019134184A1
WO2019134184A1 PCT/CN2018/072336 CN2018072336W WO2019134184A1 WO 2019134184 A1 WO2019134184 A1 WO 2019134184A1 CN 2018072336 W CN2018072336 W CN 2018072336W WO 2019134184 A1 WO2019134184 A1 WO 2019134184A1
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zirconium
mol
extracting
hydrochloric acid
hafnium
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PCT/CN2018/072336
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English (en)
French (fr)
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徐志高
何宏杨
徐斐
吴明
张文杰
何正艳
张蓉
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中南民族大学
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Priority to US16/203,984 priority Critical patent/US20200024151A1/en
Publication of WO2019134184A1 publication Critical patent/WO2019134184A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/40—Mixtures
    • C22B3/409—Mixtures at least one compound being an organo-metallic compound
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G27/00—Compounds of hafnium
    • C01G27/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G27/00—Compounds of hafnium
    • C01G27/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/14—Obtaining zirconium or hafnium

Definitions

  • the invention relates to the technical field of purification, in particular to a method for extracting and separating zirconium and hafnium in a hydrochloric acid medium.
  • Zirconium and hafnium are always symbiotic in nature. Generally, commercially available zirconium chemicals have less cerium content (m Hf /m (Zr+Hf) ) (generally 1% to 3%), and if the separation is carried out, the extraction agent with preferential extraction of hydrazine will have a larger The advantages. Due to the "tether system shrinkage", the atomic radii and ionic radii of zirconium and hafnium are basically the same, the physicochemical properties are very similar, and separation from each other is very difficult, and it is considered to be one of the most difficult elements to be separated in the periodic table.
  • zirconium has a small absorption cross section for thermal neutrons and is widely used as a nuclear reactor cladding and structural material.
  • the content of niobium in nuclear grade zirconium is less than 0.01%, while niobium has a large heat.
  • the sub-absorption section is mainly used as a neutron control rod for nuclear reactions, and the zirconium content in the core grade is less than 2%. Therefore, zirconium and hafnium separation is the key to obtaining nuclear grade zirconium and hafnium materials.
  • Nuclear power is a cost-effective, clean energy source that does not emit sulfur dioxide, soot, nitrogen oxides and carbon dioxide. Replacing part of thermal power with nuclear power will not only reduce the total amount of coal mining, transportation and combustion, but also an effective way to reduce pollutants in the power industry. It is also an important measure to slow down the global warming effect.
  • countries have been vigorously developing nuclear power, promoting the development and attention of zirconium and hafnium separation technology, and developing various zirconium and hafnium separation methods, such as molten salt distillation, ion exchange and solvent extraction.
  • the solvent extraction method has a series of outstanding advantages such as fast equilibrium speed, good separation effect, large processing capacity, easy operation and low cost, it is the main method for separation of zirconium and hafnium.
  • the extraction system there is a neutral extraction system and acid extraction.
  • System alkaline extraction system, chelation extraction system and synergistic extraction system.
  • the extracted extractants and extraction systems are only MIBK, Cyanex 301, Cyanex 302 and D2EHPA, etc., which are preferentially extracted from zirconium chemicals, except for MIBK, which extracts dilute solution ( ⁇ 10g/L zirconium). Not conducive to industrial applications.
  • the MIBK method was developed in the United States in the 1970s for industrial production. Nearly two-thirds of the world's nuclear grade zirconium lanthanum is produced by this method.
  • the MIBK method preferentially extracts cerium in the zirconium lanthanum in the presence of SCN - in the presence of less than cerium, while the more abundant zircon remains in the aqueous phase, thereby separating zirconium and hafnium (the separation factor for zirconium lanthanum is about 9) ), the extractant has a large capacity and high efficiency.
  • MIBK has some disadvantages: (1) MIBK has a solubility in water of up to 1.7 wt% (one of the most soluble extractants in water) and a large solvent loss; (2) the use of unstable thiocyanate (and thiocyanate) is required. Salt), easily decomposed into toxic decomposition products under acidic conditions, such as hydrogen sulfide, methyl mercaptan and CN- , etc., polluting the environment; (3) MIBK has a certain smell, making the operating workshop environment worse; (4) MIBK flash Low point, easy to cause fire.
  • the drawbacks of the MIBK process indicate the need for improvement or replacement.
  • DIBK Diisobutyl ketone
  • MIBK Diisobutyl ketone
  • MIBK is a neutral oxygen-containing extractant similar in structure to MIBK. Both have similar extraction properties and similar extraction mechanisms. The structural differences lead to differences in the properties of the extractant. For example, the flash point of DIBK is 47 ° C, while the flash point of MIBK is only 22.78 ° C; the water solubility of DIBK is 0.043 wt%, and the MIBK is as high as 1.7 wt%. It is precisely because of these shortcomings of the MIBK method that its industrial applications are limited.
  • DIBK diisobutyl ketone
  • the object of the present invention is to provide a method for extracting and separating zirconium and hafnium in a hydrochloric acid medium, which can realize the clean production of the zirconium and hafnium separation process without using toxic substances in the separation process.
  • the extractant is mixed with an acidic liquid formed by mixing zirconium chemicals and hydrochloric acid, and the extracted raffinate is mixed with a base to obtain a zirconium hydroxide precipitate, and the organic phase containing ruthenium is supported.
  • the stripping solution is mixed with a base to obtain cerium hydroxide precipitate, calcined zirconium hydroxide precipitate and cerium hydroxide precipitate, and the extracting agent comprises a mixture of DIBK and a phosphonic acid extracting agent (containing a CP bond).
  • the phosphonic acid extractant (containing a C-P bond) is at least one selected from the group consisting of Cyanex 921, Cyanex 923, Cyanex 925, and Cyanex 572.
  • the extractant is pre-extracted with hydrochloric acid prior to extraction.
  • the concentration of hydrochloric acid in the pre-extraction is from 1.0 to 4.0 mol/L, and/or, in the case of pre-extraction, the extracting agent is carried out in an equal volume with hydrochloric acid.
  • the acidic liquid further comprises an inorganic salt.
  • the zirconium chemical is mixed with hydrochloric acid to form an acidic liquid
  • the extracting agent is used to extract the acidic liquid
  • the phase separation is followed to obtain a raffinate and a supported organic phase containing ruthenium
  • the raffinate is mixed with the alkali.
  • a mixture of extractants including CP bonds).
  • the beneficial effects of the embodiments of the present invention include: a synergistic system composed of DIBK and Cyanex 923 or a synergistic system composed of DIBK and a phosphonic acid extractant (including a CP bond) preferentially extracting a relatively small amount of cerium in a mixed solution of zirconium and cerium, thus Low mass transfer, large extraction capacity; simple process, easy operation, high extraction efficiency, and no need to use highly toxic substances such as thiocyanate or its salt in this separation process, the whole separation process is clean.
  • Zirconium and hafnium are always symbiotic in nature. Generally, commercially available zirconium chemicals have less cerium content (m Hf /m (Zr+Hf) ) (generally 1% to 3%), and if the separation is carried out, the extraction agent with preferential extraction of hydrazine will have a larger The advantages. Due to the "tether system shrinkage", the atomic radii and ionic radii of zirconium and hafnium are basically the same, the physicochemical properties are very similar, and separation from each other is very difficult, and it is considered to be one of the most difficult elements to be separated in the periodic table.
  • zirconium has a small absorption cross section for thermal neutrons and is widely used as a nuclear reactor cladding and structural material.
  • the content of niobium in nuclear grade zirconium is less than 0.01%, while niobium has a large heat.
  • the sub-absorption section is mainly used as a neutron control rod for nuclear reactions, and the zirconium content in the core grade is less than 2%. Therefore, zirconium and hafnium separation is the key to obtaining nuclear grade zirconium and hafnium materials.
  • the present invention provides a method for extracting and separating zirconium and hafnium in a hydrochloric acid medium, which is mainly used for achieving efficient separation of zirconium and hafnium, and includes the following steps:
  • the concentration of each component in the obtained acidic liquid is controlled, for example:
  • the total concentration of zirconium ions and strontium ions in the feed liquid is less than 0.05 mol/L, although it is advantageous for the separation of zirconium and hafnium, the amount of the liquid treatment is large, and the total amount of consumed acid is large. If the total concentration of zirconium ions and strontium ions in the feed liquid is higher than 2.0 mol/L, when the total free acidity is less than 0.05 mol/L, the zirconium lanthanum is easily hydrolyzed, and the separation efficiency is poor; when the total free acidity is greater than 4.0 mol/L, The zirconium-niobium separation factor is reduced.
  • the total concentration of zirconium ions and cerium ions in the liquid solution is preferably from 0.05 to 2.0 mol/L; preferably from 0.5 to 1.5 mol/L, more preferably from 1.0 to 1.5 mol/L.
  • the total free acidity of the feed liquid is from 0.5 to 4.0 mol/L, preferably from 1.0 to 2.5 mol/L.
  • the chloride ion concentration is preferably controlled to be 0.5-5.0 mol/L.
  • an inorganic salt may be introduced into the acidic liquid, and when the sulfate is added as the inorganic salt in the acidic liquid.
  • Sulfate ion can also be introduced, and the sulfate ion concentration is preferably controlled to be 0 to 1.25 mol/L, for example, the sulfate ion concentration is 0.2 mol/L, 0.4 mol/L, 0.5 mol/L, 0.6 mol/L, 0.8 mol. /L, 1.0 mol/L and 1.25 mol/L, and the like.
  • the acidic liquid may also be added with ammonia or the like for adjusting the pH in the acidic liquid.
  • the extracted acid solution is extracted by using an extractant, wherein the extractant comprises a synergistic system formed by DIBK and DIBK and a phosphonic acid extractant (containing a CP bond), and the phosphonic acid extractant is selected from Cyanex 921, Cyanex 923, Cyanex 925 and At least one of the groups consisting of Cyanex572, that is, a synergistic system formed by DIBK and Cyanex 921, a synergistic system formed by DIBK and Cyanex 923, a synergistic system formed by DIBK and Cyanex 925, or a DIBK.
  • the extractant comprises a synergistic system formed by DIBK and DIBK and a phosphonic acid extractant (containing a CP bond)
  • the phosphonic acid extractant is selected from Cyanex 921, Cyanex 923, Cyanex 925 and At least one of the groups consisting of Cyanex572, that is, a synergistic system
  • a synergistic system formed with Cyanex 572 in some embodiments of the present invention, a synergistic system formed by DIBK with Cyanex 921, Cyanex 923, Cyanex 925, and Cyanex 572 can also be used, which is synergistic with liquid-liquid extraction using a single extractant. Extraction is more efficient.
  • DIBK diisobutyl ketone
  • the volume content of the phosphonic acid extractant is preferably 2 % to 40%, more preferably 2% to 20%.
  • an extractant similar in nature to Cyanex 921 or Cyanex 923 or Cyanex 925 or Cyanex 572 may be used instead of Cyanex 921 or Cyanex 923 or Cyanex 925 or Cyanex 572, and other extracting agents having similar properties may be further added.
  • Phosphonic acid extractant (including CP bond) is an organic phosphine oxide extractant.
  • the zirconium and hafn separation coefficient ⁇ value increases with the increase of the volume percentage of phosphonic acid extractant (including CP bond).
  • the concentration ratio of the phosphonic acid extractant (including CP bond) is more than 40%, the extraction amount of zirconium is too large, which is disadvantageous for the separation of zirconium and hafnium, so the content thereof is preferably 2-20%.
  • the mixing time of the two phases is 2 to 30 minutes, preferably 5 to 15 minutes
  • the temperature in the tank of the extraction tank is It is preferably controlled between 0 and 40 ° C, for example, 5 ° C, 10 ° C, 15 ° C, 20 ° C, 25 ° C, 30 ° C, and 35 ° C.
  • Hf 4+ and Zr 4+ are both hard acids, but Hf 4+ is more acidic than Zr 4+ acid, and it is easier to form a more stable complex with hard base extractants.
  • the phosphonic acid extractant (including the CP bond) is stronger than the Lewis extract of the phosphate extractant (including the COP bond), and is more likely to form a more stable extract with Hf 4+ having a smaller ionic radius, that is, it is easier to be extraction.
  • the strong selectivity of DIBK with large steric hindrance is combined with the phosphonic acid extractant (including CP bond) to preferentially extract ruthenium, which can significantly improve the extraction rate of ruthenium and the separation efficiency of zirconium and hafnium.
  • the extractant may be diluted and mixed with a diluent in advance, and the diluent may be selected from the group consisting of sulfonated kerosene, hexane, isooctane, and 200# solvent oil, etc., it should be understood that the diluent may be composed of the above substances. One or at least two components.
  • the extractant is mixed with hydrochloric acid for pre-extraction, wherein the concentration of hydrochloric acid is preferably 1.0-4.0 mol/L, for example, 1.0 mol/L, 1.5 mol/L, 2.0 mol/L, 2.5 mol/L, 3.0 mol/L. , 3.5 mol / L, 4.0 mol / L and the like.
  • concentration of hydrochloric acid is preferably 1.0-4.0 mol/L, for example, 1.0 mol/L, 1.5 mol/L, 2.0 mol/L, 2.5 mol/L, 3.0 mol/L. , 3.5 mol / L, 4.0 mol / L and the like.
  • the effect of pre-extraction is to bring the extractant to a pre-saturation state.
  • the extractant is pre-extracted and used as an organic phase, and the acidic feed liquid is used as an aqueous phase, and mixed for extraction.
  • the zirconium remains in the raffinate aqueous phase to obtain a zirconium solution having no antimony or less antimony, and hydrazine in the aqueous phase. Entering the organic phase gives a supported organic phase containing ruthenium.
  • the obtained zirconium-free zirconium solution is precipitated with a base (for example, ammonia water, caustic soda, etc.) to obtain zirconium hydroxide precipitate.
  • a base for example, ammonia water, caustic soda, etc.
  • the ruthenium-containing supported organic phase is back-extracted with a carbonate.
  • the carbonate may be sodium carbonate, potassium carbonate, magnesium carbonate, and aluminum carbonate.
  • the carbonate may be the above.
  • the hydrazine enters the aqueous phase, and the resulting stripping solution is a cerium-rich solution.
  • the weight ratio of m Hf /m (Hf + Zr) is 10% to 40%.
  • the carbonate concentration for stripping may be, for example, 0.05 to 5.0 mol/L.
  • cerium-rich solution is then precipitated with a base (e.g., aqueous ammonia, caustic soda, etc.) to obtain a cerium hydroxide precipitate.
  • a base e.g., aqueous ammonia, caustic soda, etc.
  • the obtained zirconium hydroxide precipitate and the cesium hydroxide precipitate are washed with deionized water, and the washed zirconium hydroxide and cesium hydroxide are precipitated and calcined, preferably, the calcination temperature is 850-1800 ° C, for example, at 850 ° C, The calcination is carried out at 1000 ° C, 1200 ° C, 1400 ° C, 1600 ° C and 1800 ° C, and the calcination can also be carried out in a gradient heating manner.
  • zirconia After calcination, zirconia is obtained as an atomic level, and zirconium-containing cerium oxide can also reach atomic energy level after further separation.
  • the present invention provides a method for extracting and separating zirconium and hafnium in a hydrochloric acid medium, which is mainly used for achieving high-efficiency separation of zirconium and hafnium, which is substantially the same as the above separation method, except that the acidic liquid solution Prepared before extraction:
  • the raw material containing zirconium and hafnium to be separated is made into an acidic liquid, that is, the zirconium chemical is mixed with hydrochloric acid to form an acidic liquid.
  • an inorganic salt may be added to the acidic liquid, and the inorganic salt may be selected from chlorine. At least one of the group consisting of ammonium chloride, sodium chloride, magnesium chloride, ammonium sulfate, sodium sulfate, and magnesium sulfate.
  • the acidic feed may also be added with a quantity of aqueous ammonia to adjust the pH in the feed.
  • the acidic liquid can be obtained, for example, as follows:
  • Zirconite is prepared by direct boiling chlorination of carbonized, chlorinated or zircon, and zirconium tetrachloride is dissolved in water. Ammonia water and inorganic salts are added to prepare an acidic liquid, wherein ammonia and inorganic salts can be used. Quantitative addition.
  • Zircon is leached by alkali fusion, water washing, dilute hydrochloric acid, and quantitative hydrochloric acid and inorganic salt are added to prepare an acidic liquid.
  • the zirconium oxychloride is directly dissolved in water, and a quantitative amount of hydrochloric acid and an inorganic salt are added to prepare an acidic liquid.
  • raw materials of zirconium oxide or zirconium oxide or cerium oxide or metal cerium, or zirconium waste or strontium waste containing other impurities The raw material is prepared according to the first or second method, and the quantitative hydrochloric acid and inorganic salt are added to prepare an acidic material. liquid.
  • the composition of the aqueous phase is 1.5 mol/L of the initial zirconium ion, wherein the concentration of barium ion is about 0.018 mol/L, the acidity of the aqueous phase is 1.7 mol/L, (NH 4 ) 2 SO 4 The concentration was 0.8 mol/L.
  • the extractant is a premixed extractant with an equal volume of 3.5 mol/L hydrochloric acid, using a mixed organic phase consisting of 90% (v/v) DIBK and 10% (v/v) Cyanex 923.
  • the pre-extracted extractant is used as the organic phase
  • the acidic feed liquid is used as the aqueous phase
  • the control (organic phase: aqueous phase) is 2:1
  • the feed liquid is subjected to single-stage extraction at room temperature, and the mixing time of the two phases is 10
  • the zirconium remains in the raffinate to obtain a zirconium solution with less ruthenium, and then the zirconium solution is precipitated with ammonia water to obtain a zirconium hydroxide precipitate, and the ruthenium in the feed liquid is all extracted into the organic phase to obtain ruthenium.
  • Loaded organic phase
  • zirconium hydroxide and barium hydroxide precipitates were respectively washed with deionized water, and the washed zirconium hydroxide and barium hydroxide precipitates were respectively calcined at 1200 ° C to obtain less zirconium oxide and zirconium oxide-containing barium oxide product.
  • the total concentration of zirconium and hafnium metal ions in the aqueous phase before and after extraction was determined by EDTA standard droplet method.
  • the acidity was determined by sodium hydroxide standard droplet method.
  • the concentration of rhodium was determined by ICP-MS method, and then the organic phase was calculated by subtraction method.
  • the total concentration of zirconium and hafnium metal ions and the concentration of barium ions were used to calculate the partition ratio, separation factor and extraction rate.
  • the concentration of metal ions in the organic phase, the distribution ratio of zirconium and hafnium, the separation factor and the extraction rate are calculated as follows:
  • V a , V o - the volume of the aqueous phase and the organic phase, respectively, mL;
  • D r(Zr) , D r(Hf) - the distribution ratio of zirconium and hafnium, respectively;
  • ⁇ is the separation factor of zirconium and hafnium
  • E Zr and E Hf are the extraction rates of organic relative zirconium and hafnium, respectively.
  • the extraction ratio of the system to ruthenium is 82.50%, while the extraction rate of zirconium is 14.50%, and the separation coefficient of zirconium lanthanum is 27.
  • the organic phase consisted of 90% (v/v) DIBK, 2% (v/v) Cyanex 921 and 8% (v/v) sulfonated kerosene (as a diluent) with an equal volume of 3.4 mol/L in advance.
  • the hydrochloric acid is pre-extracted once, and the aqueous phase composition is the initial concentration of the initial zirconium ions of 1.5 mol/L, wherein the cesium ion concentration is 0.018 mol/L, the aqueous phase acidity is 1.7 mol/L, and the (NH 4 ) 2 SO 4 addition amount is 0.8mol/L, the control ratio is 2:1, single-stage extraction is carried out at room temperature, the mixing time of the two phases is 5 minutes, the raffinate and the supported organic phase containing ruthenium are obtained after phase separation, and the raffinate is reused with ammonia water.
  • the extraction rate for rhodium is 58.98%, the extraction ratio of zirconium is 11.03%, and the separation factor of zirconium and hafnium is 10.
  • the organic phase consisted of 90% (v/v) DIBK, 8% (v/v) Cyanex 923 and 2% (v/v) isooctane (as a diluent) with an equal volume of 4.0 mol/L in advance.
  • the hydrochloric acid is pre-extracted once, and the aqueous phase composition is the initial concentration of zirconium ions of 1.0 mol/L, wherein the concentration of cerium ions is 0.012 mol/L, the acidity of the aqueous phase is 2.0 mol/L, and the amount of (NH 4 ) 2 SO 4 is 0.8mol/L, the control ratio is 2:1, single-stage extraction is carried out at room temperature, the mixing time of the two phases is 5 minutes, the raffinate and the supported organic phase containing ruthenium are obtained after phase separation, and the raffinate is reused with ammonia water.
  • the extraction ratio of ruthenium was 54.98%, the extraction rate of zirconium was 14.51%, and the separation coefficient of zirconium lanthanum was 7.
  • the organic phase consisted of 60% (v/v) DIBK and 40% (v/v) Cyanex 925, and was pre-extracted once with oil-water ratio of 1:3 of 1.0 mol/L hydrochloric acid, and the aqueous phase composition was initial zirconium.
  • the total concentration of cerium ions is 0.5mol/L, wherein the cerium ion concentration is 0.006mol/L, the aqueous phase acidity is 1.0mol/L, and the (NH 4 ) 2 SO 4 is 0.6mol/L.
  • the control ratio is 2:1. Single-stage extraction is carried out at room temperature, and the mixing time of the two phases is 2 minutes.
  • the raffinate and the supported organic phase containing ruthenium are obtained, and the raffinate is precipitated with sodium hydroxide to obtain a precipitate of zirconium hydroxide with less bismuth.
  • the supported organic phase was stripped with 3.0 mol/L potassium carbonate, the ratio of washing and stripping was 1:2, and the mixing time of the two phases was 5 minutes to obtain a zirconium-rich cerium solution, wherein the cerium-rich solution In the weight ratio of m Hf /m (Hf + Zr) is 10%.
  • Precipitation was carried out using sodium hydroxide to obtain a zirconium hydroxide precipitate containing zirconium.
  • the other operation steps are the same as in the first embodiment.
  • the extraction ratio of ruthenium was 64.66%, the extraction rate of zirconium was 14.21%, and the separation coefficient of zirconium lanthanum was 8.
  • the organic phase consisted of 80% (v/v) DIBK and 20% (v/v) Cyanex 923, and pre-extracted with an equal volume of 2.4 mol/L hydrochloric acid in advance, and the aqueous phase composition was the initial zirconium ion total concentration of 1.0. Mol/L, wherein the cesium ion concentration is 0.012 mol/L, the aqueous phase acidity is 1.2 mol/L, the (NH 4 ) 2 SO 4 is added in an amount of 1.25 mol/L, and the control ratio is 2:1, at room temperature.
  • Single-stage extraction, mixing time of two phases is 30 minutes, after phase separation, the raffinate and the supported organic phase containing ruthenium are obtained, and the raffinate is precipitated with ammonia water to obtain a precipitate of zirconium hydroxide with less ruthenium;
  • the mol/L magnesium carbonate is stripped, the washing and stripping are both 1:2, and the two-phase mixing time is 5 minutes to obtain a zirconium-rich cerium solution, wherein, in the cerium-rich solution, m Hf /m ( The weight ratio of Hf + Zr) is 15%.
  • Precipitation was carried out with aqueous ammonia to obtain a zirconium hydroxide precipitate containing zirconium.
  • the other operation steps are the same as in the first embodiment.
  • the extraction ratio of ruthenium was 68.22%, the extraction rate of zirconium was 12.25%, and the separation factor of zirconium lanthanum was 12.
  • the organic phase consisted of 70% (v/v) DIBK and 30% (v/v) Cyanex 923, and pre-extracted with an equal volume of 4.0 mol/L hydrochloric acid in advance, and the aqueous phase composition was the initial total zirconium ion concentration of 2.0. Mol/L, wherein the concentration of cesium ions is 0.024 mol/L, the acidity of the aqueous phase is 2.0 mol/L, the amount of (NH 4 ) 2 SO 4 is 1.0 mol/L, and the control ratio is 2:1, at room temperature.
  • the extraction ratio of ruthenium was 70.78%, the extraction rate of zirconium was 13.64%, and the separation factor of zirconium lanthanum was 15.
  • the organic phase consisted of 85% (v/v) DIBK and 15% (v/v) Cyanex 925, and pre-extracted with an equal volume of 4.0 mol/L hydrochloric acid in advance, and the aqueous phase composition was the initial concentration of 0.5 zirconium ions.
  • Mol/L wherein the cesium ion concentration is 0.006 mol/L, the aqueous phase acidity is 2.0 mol/L, the (NH 4 ) 2 SO 4 is 0.8 mol/L, and the control ratio is 2:1, at room temperature.
  • the mixing time of the two phases is 10 minutes, after the phase separation, the raffinate and the supported organic phase containing ruthenium are obtained, and the raffinate is precipitated with ammonia water to obtain a precipitate of zirconium hydroxide with less ruthenium;
  • the mol/L sodium carbonate is stripped, the washing and stripping are both 1:2, and the two-phase mixing time is 10 minutes to obtain a zirconium-rich cerium solution, wherein, in the cerium-rich solution, m Hf /m ( The weight ratio of Hf + Zr) is 20%.
  • Precipitation was carried out with aqueous ammonia to obtain a zirconium hydroxide precipitate containing zirconium.
  • the other operation steps are the same as in the first embodiment.
  • the extraction ratio of ruthenium was 68.42%, the extraction rate of zirconium was 12.68%, and the separation factor of zirconium lanthanum was 16.
  • the organic phase consisted of 65% (v/v) DIBK and 35% (v/v) Cyanex 923, and pre-extracted with an equal volume of 3.4 mol/L hydrochloric acid in advance, and the aqueous phase composition was the initial concentration of 1.2 zirconium ions. Mol/L, wherein the cesium ion concentration is 0.015 mol/L, the aqueous acidity is 1.7 mol/L, the (NH 4 ) 2 SO 4 is 0.8 mol/L, and the control ratio is 2:1, at room temperature.
  • Single-stage extraction, two-phase mixing time is 15 minutes, after phase separation, the raffinate and the supported organic phase containing ruthenium are obtained, and the raffinate is precipitated with ammonia water to obtain a precipitate of zirconium hydroxide with less ruthenium;
  • the mol/L sodium carbonate is stripped, the washing and stripping are both 1:2, and the two-phase mixing time is 15 minutes to obtain a zirconium-rich cerium solution, wherein, in the cerium-rich solution, m Hf /m ( The weight ratio of Hf + Zr) is 35%.
  • Precipitation was carried out with aqueous ammonia to obtain a zirconium hydroxide precipitate containing zirconium.
  • the other operation steps are the same as in the first embodiment.
  • the extraction ratio of ruthenium was 82.50%, the extraction ratio of zirconium was 14.50%, and the separation coefficient of zirconium lanthanum was 28.
  • the organic phase consisted of 90% (v/v) DIBK and 2% (v/v) Cyanex 923 and 8% (v/v) hexane, and pre-extracted with an equal volume of 2.0 mol/L hydrochloric acid.
  • the composition of the aqueous phase is 1.5mol/L of the initial zirconium and cerium ions, wherein the concentration of cerium ions is 0.018mol/L, the acidity of the aqueous phase is 1.0mol/L, and the amount of (NH 4 ) 2 SO 4 is 0.4mol/L.
  • single-stage extraction was carried out at room temperature, and the mixing time of the two phases was 5 minutes.
  • the raffinate and the supported organic phase containing ruthenium were obtained, and the raffinate was precipitated with ammonia water to obtain less ruthenium.
  • Ammonia water was precipitated to obtain a zirconium hydroxide precipitate containing zirconium.
  • the other operation steps are the same as in the first embodiment.
  • the extraction ratio of ruthenium was 62.55%, the extraction rate of zirconium was 11.84%, and the separation coefficient of zirconium lanthanum was 8.
  • the organic phase consisted of 90% (v/v) DIBK and 8% (v/v) Cyanex 923 and 2% (v/v) 200# solvent, and pre-extracted with an equal volume of 4.0 mol/L hydrochloric acid.
  • the composition of the aqueous phase is the initial concentration of zirconium ions of 2.0 mol/L, wherein the concentration of cerium ions is 0.024 mol/L, the acidity of the aqueous phase is 1.9 mol/L, and the amount of (NH 4 ) 2 SO 4 is 0.8 mol/L.
  • the control ratio is 2:1, single-stage extraction is carried out at room temperature, and the mixing time of the two phases is 10 minutes.
  • the raffinate and the supported organic phase containing ruthenium are obtained, and the raffinate is precipitated with ammonia water to obtain less ruthenium.
  • Precipitation was carried out with aqueous ammonia to obtain a zirconium hydroxide precipitate containing zirconium.
  • the other operation steps are the same as in the first embodiment.
  • the extraction ratio of ruthenium was 68.44%, the extraction rate of zirconium was 12.62%, and the separation coefficient of zirconium lanthanum was 9.
  • the organic phase consisted of 90% (v/v) DIBK and 10% (v/v) Cyanex 925, and pre-extracted with an equal volume of 3.0 mol/L hydrochloric acid in advance, and the aqueous phase composition was the initial concentration of 1.5 zirconium ions.
  • Mol/L wherein the cesium ion concentration is 0.018 mol/L, the aqueous phase acidity is 1.5 mol/L, the (NH 4 ) 2 SO 4 is 0.4 mol/L, and the control ratio is 2:1, at room temperature.
  • Single-stage extraction, mixing time of two phases is 10 minutes. After phase separation, the raffinate and the supported organic phase containing ruthenium are obtained.
  • the raffinate is precipitated with ammonia water to obtain zirconium hydroxide precipitate; the supported organic phase is 1.0 mol/L.
  • Potassium carbonate was subjected to stripping, the ratio of washing and stripping was 1:2, and the mixing time of the two phases was 10 minutes to obtain a zirconium-rich cerium solution, which was precipitated with ammonia water to obtain a zirconium hydroxide-containing precipitate.
  • the other operation steps are the same as in the first embodiment.
  • the extraction rate for rhodium is 58.98%, the extraction ratio of zirconium is 11.03%, and the separation factor of zirconium and hafnium is 10.
  • the organic phase consisted of 90% (v/v) DIBK, 2% (v/v) Cyanex 572 and 8% (v/v) sulfonated kerosene (as a diluent) with an equal volume of 2.8 mol/L in advance.
  • the hydrochloric acid is pre-extracted once, and the aqueous phase composition is the initial concentration of the initial zirconium ions of 1.5 mol/L, wherein the cesium ion concentration is 0.018 mol/L, the aqueous phase acidity is 1.4 mol/L, and the (NH 4 ) 2 SO 4 addition amount is 0.6mol/L, the control ratio is 2:1, single-stage extraction is carried out at room temperature, the mixing time of the two phases is 5 minutes, and the raffinate and the supported organic phase containing ruthenium are obtained after phase separation, and the raffinate is reused with ammonia water.
  • the extraction ratio of ruthenium was 44.81%, the extraction rate of zirconium was 11.22%, and the separation factor of zirconium lanthanum was 7.
  • the organic phase consisted of 90% (v/v) DIBK, 8% (v/v) Cyanex 572 and 2% (v/v) sulfonated kerosene (as a diluent) with an equal volume of 2.8 mol/L in advance.
  • the hydrochloric acid is pre-extracted once, and the aqueous phase composition is the initial concentration of the initial zirconium ions of 1.5 mol/L, wherein the cesium ion concentration is 0.018 mol/L, the aqueous phase acidity is 1.4 mol/L, and the (NH 4 ) 2 SO 4 addition amount is 0.6mol/L, the control ratio is 2:1, single-stage extraction is carried out at room temperature, the mixing time of the two phases is 5 minutes, and the raffinate and the supported organic phase containing ruthenium are obtained after phase separation, and the raffinate is reused with ammonia water.
  • the extraction ratio of ruthenium was 50.28%, the extraction rate of zirconium was 12.64%, and the separation coefficient of zirconium lanthanum was 10.
  • the organic phase consisted of 60% (v/v) DIBK and 40% (v/v) Cyanex572, and was pre-extracted once with an equal volume of 3.0 mol/L hydrochloric acid.
  • the aqueous phase composition was the initial concentration of 0.5 zirconium ions. Mol/L, wherein the cesium ion concentration is 0.006 mol/L, the aqueous phase acidity is 1.5 mol/L, the NH 4 Cl is 0.6 mol/L, and the control ratio is 2:1, and single-stage extraction is performed at room temperature. The mixing time of the two phases is 2 minutes.
  • the raffinate and the supported organic phase containing ruthenium are obtained, and the raffinate is precipitated with sodium hydroxide to obtain a precipitate of zirconium hydroxide with less ruthenium; the supported organic phase is 3.0 mol/ L potassium carbonate is stripped, the ratio of washing and stripping is 1:2, and the mixing time of the two phases is 5 minutes to obtain a zirconium-rich cerium solution, wherein, in the cerium-rich solution, m Hf /m (Hf+ The weight ratio of Zr) is 13%.
  • Precipitation was carried out using sodium hydroxide to obtain a zirconium hydroxide precipitate containing zirconium.
  • the other operation steps are the same as in the first embodiment.
  • the extraction ratio of ruthenium was 52.42%, the extraction rate of zirconium was 13.22%, and the separation coefficient of zirconium lanthanum was 8.
  • the organic phase consisted of 80% (v/v) DIBK and 20% (v/v) Cyanex 923, and pre-extracted with an equal volume of 3.2 mol/L hydrochloric acid in advance, and the aqueous phase composition was the initial concentration of initial zirconium ions 1.0. Mol/L, wherein the cesium ion concentration is 0.012 mol/L, the aqueous phase acidity is 1.6 mol/L, the (NH 4 ) 2 SO 4 is 1.25 mol/L, and the control ratio is 2:1, at room temperature.
  • Single-stage extraction, mixing time of two phases is 30 minutes, after phase separation, the raffinate and the supported organic phase containing ruthenium are obtained, and the raffinate is precipitated with ammonia water to obtain a precipitate of zirconium hydroxide with less ruthenium;
  • the mol/L magnesium carbonate is stripped, the washing and stripping are both 1:2, and the two-phase mixing time is 5 minutes to obtain a zirconium-rich cerium solution, wherein, in the cerium-rich solution, m Hf /m ( The weight ratio of Hf + Zr) is 30%.
  • Precipitation was carried out with aqueous ammonia to obtain a zirconium hydroxide precipitate containing zirconium.
  • the other operation steps are the same as in the first embodiment.
  • the extraction ratio of ruthenium was 70.58%, the extraction ratio of zirconium was 11.53%, and the separation factor of zirconium lanthanum was 18.
  • the organic phase consisted of 70% (v/v) DIBK and 30% (v/v) Cyanex 921, and pre-extracted with an equal volume of 4.0 mol/L hydrochloric acid in advance, and the aqueous phase composition was the initial total concentration of zirconium ions.
  • Mol/L wherein the cesium ion concentration is 0.024 mol/L, the aqueous phase acidity is 2.0 mol/L, the (NH 4 ) 2 SO 4 is 0.8 mol/L, and the control ratio is 2:1, at room temperature.
  • the extraction ratio of ruthenium was 73.06%, the extraction rate of zirconium was 11.66%, and the separation factor of zirconium lanthanum was 18.
  • the organic phase consisted of 85% (v/v) DIBK and 15% (v/v) Cyanex572, and pre-extracted with an equal volume of 2.8 mol/L hydrochloric acid in advance.
  • the aqueous phase composition was the initial concentration of initial zirconium ions. Mol/L, wherein the cesium ion concentration is 0.0006 mol/L, the aqueous phase acidity is 1.4 mol/L, the (NH 4 ) 2 SO 4 is 0.8 mol/L, and the control ratio is 2:1, at room temperature.
  • the mixing time of the two phases is 10 minutes, after the phase separation, the raffinate and the supported organic phase containing ruthenium are obtained, and the raffinate is precipitated with ammonia water to obtain a precipitate of zirconium hydroxide with less ruthenium;
  • the mol/L sodium carbonate is stripped, the washing and stripping are both 1:2, and the two-phase mixing time is 10 minutes to obtain a zirconium-rich cerium solution, wherein, in the cerium-rich solution, m Hf /m ( The weight ratio of Hf + Zr) is 15%.
  • Precipitation was carried out with aqueous ammonia to obtain a zirconium hydroxide precipitate containing zirconium.
  • the other operation steps are the same as in the first embodiment.
  • the extraction ratio of ruthenium was 48.32%, the extraction rate of zirconium was 11.68%, and the separation coefficient of zirconium lanthanum was 10.
  • the organic phase consisted of 65% (v/v) DIBK and 35% (v/v) Cyanex572, and pre-extracted with an equal volume of 3.0 mol/L hydrochloric acid in advance, and the aqueous phase composition was the initial concentration of initial zirconium ions 1.0. Mol/L, wherein the cesium ion concentration is 0.012 mol/L, the aqueous phase acidity is 1.5 mol/L, the MgCl 2 is 0.4 mol/L, the control ratio is 2:1, and the single-stage extraction is performed at room temperature. The mixing time is 15 minutes. After phase separation, the raffinate and the supported organic phase containing ruthenium are obtained.
  • the raffinate is precipitated with ammonia water to obtain a precipitate of zirconium hydroxide with less lanthanum; the organic phase is loaded with 1.5 mol/L sodium carbonate.
  • the ratio of washing and stripping is 1:2, and the mixing time of the two phases is 15 minutes to obtain a zirconium-rich cerium solution, wherein, in the cerium-rich solution, m Hf /m (Hf+Zr) The weight ratio is 13%.
  • Precipitation was carried out with aqueous ammonia to obtain a zirconium hydroxide precipitate containing zirconium.
  • the other operation steps are the same as in the first embodiment.
  • the extraction ratio of ruthenium was 48.48%, the extraction rate of zirconium was 12.24%, and the separation coefficient of zirconium lanthanum was 8.
  • the organic phase consisted of 90% (v/v) DIBK and 8% (v/v) Cyanex 923 and 2% (v/v) Cyanex 923, and pre-extracted once with an equal volume of 3.6 mol/L hydrochloric acid.
  • the phase composition is the total concentration of initial zirconium ions of 1.5mol/L, wherein the concentration of cerium ions is 0.018mol/L, the acidity of aqueous phase is 1.8mol/L, and the amount of (NH 4 ) 2 SO 4 is 0.8mol/L.
  • the ratio is 2:1, single-stage extraction is carried out at room temperature, and the mixing time of the two phases is 5 minutes.
  • the raffinate and the supported organic phase containing ruthenium are obtained, and the raffinate is precipitated with ammonia water to obtain hydrogen with less ruthenium.
  • Precipitation was carried out to obtain a zirconium hydroxide precipitate containing zirconium.
  • the other operation steps are the same as in the first embodiment.
  • the extraction ratio of ruthenium was 82.48%, the extraction ratio of zirconium was 10.20%, and the separation coefficient of zirconium lanthanum was 36.
  • the organic phase consisted of 90% (v/v) DIBK and 8% (v/v) Cyanex 572 and 2% (v/v) isooctane, and was pre-extracted with an equal volume of 2.8 mol/L hydrochloric acid.
  • the composition of the aqueous phase is the initial concentration of zirconium ions of 2.0 mol/L, wherein the concentration of cerium ions is 0.024 mol/L, the acidity of the aqueous phase is 1.4 mol/L, and the amount of NaCl added is 0.8 mol/L.
  • the control ratio is 2: 1, single-stage extraction at room temperature, the mixing time of the two phases is 10 minutes, after the phase separation, the raffinate and the supported organic phase containing ruthenium are obtained, and the raffinate is precipitated with ammonia water to obtain a precipitate of zirconium hydroxide with less ruthenium;
  • the supported organic phase was back-extracted with 1.5 mol/L sodium carbonate.
  • the ratio of washing and stripping was 1:2, and the mixing time of the two phases was 10 minutes.
  • the zirconium-rich cerium solution was obtained and precipitated with ammonia water. Zirconium hydroxide containing zirconium precipitates.
  • the other operation steps are the same as in the first embodiment.
  • the extraction ratio of ruthenium was 45.22%, the extraction ratio of zirconium was 10.48%, and the separation coefficient of zirconium lanthanum was 9.
  • the selected synergistic system adopts 90% (v/v) DIBK, 5% (v/v) Cyanex 923 and 5 Cyanex572 of %(v/v), the other raw materials ratio, preparation method, etc. are the same.

Abstract

一种盐酸介质中萃取分离锆和铪的方法，属于物质精细分离技术领域，其主要通过DIBK和膦酸类萃取剂组成的协萃体系对锆化合物的酸性料液进行萃取，使锆进入水相，铪进入有机相实现分离，整个过程不需要使用有毒物质，达到清洁生产的目的。

Description

盐酸介质中萃取分离锆和铪的方法
相关申请的交叉引用
本申请要求于2018年01月03日提交中国专利局的申请号为2018100054194、名称为“盐酸介质中萃取分离锆和铪的方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及提纯技术领域，具体而言，涉及盐酸介质中萃取分离锆和铪的方法。
背景技术
锆铪在自然界中总是共生的。一般市售的锆化学品中铪含量(m Hf/m (Zr+Hf))较少(一般为1％～3％)，对其进行分离时如果采用优先萃取铪的萃取剂将有较大的优势。因“镧系收缩”，锆和铪的原子半径、离子半径基本相同，物理化学性质非常相似，彼此分离十分困难，被认为是元素周期表中最难分离的元素之一。但由于锆和铪具有相异的核性能，锆对热中子吸收截面小，被广泛用做核反应堆包壳和结构材料，核级锆中要求铪含量小于0.01％，而铪具有大的热中子吸收截面，主要用作核反应的中子控制棒，核级铪中要求锆含量小于2％。因此，锆铪分离是获得核级锆铪材料的技术关键。
核电是一种经济高效的清洁能源，不排放二氧化硫、烟尘、氮氧化物和二氧化碳。以核电替代部分火电，不但可以减少煤炭的开采、运输和燃烧总量，还是电力工业减排污染物的有效途径，更是减缓地球温室效应的重要措施。近年来各国都在大力发展核电，促进了锆铪分离技术的发展和关注，开发出多种锆铪分离方法，如熔盐精馏法、离子交换法和溶剂萃取法等。由于溶剂萃取法具有平衡速度快、分离效果好、处理量大、操作易连续、成本低等一系列突出优点，成为锆铪分离的主要方法，按萃取体系分，有中性萃取体系、酸性萃取体系、碱性萃取体系、螯合萃取体系和协同萃取体系。目前，已报道的萃取剂和萃取体系仅MIBK、Cyanex 301、Cyanex 302和D2EHPA等优先萃取锆化学品中含量较少的铪，除MIBK外均是对稀溶液(<10g/L锆)进行萃取，不利于工业化应用。
MIBK法是美国20世纪70年代开发应用于工业生产，全球近2/3的核级锆铪均产用该法分离锆铪。MIBK法在SCN -存在条件下盐酸介质中优先萃取锆铪中含量较少的铪，而含量较多的锆留在水相，从而实现锆和铪的分离(对锆铪的分离系数达到9左右)，萃取剂容量大、效率高。但MIBK法存在一些缺点：(1)MIBK在水中溶解度高达1.7wt％(是水中溶解度最高的萃取剂之一)，溶剂损失大；(2)需要使用不稳定的硫氰酸(和硫氰酸盐)， 在酸性条件下易分解成有毒的分解产物，如硫化氢、甲硫醇和CN -等，污染环境；(3)MIBK具有一定的气味，使得操作车间环境较差；(4)MIBK闪点低，易引起火灾。针对MIBK工艺存在的弊端，表明很有改进或取代的必要。
二异丁基酮(DIBK)是一种与MIBK结构相似的中性含氧类萃取剂，两者具有相近的萃取性能和相似的萃取机理，结构上的差别导致其作为萃取剂的性质也有差异，如DIBK的闪点47℃，而MIBK的闪点仅22.78℃；DIBK的水溶度为0.043wt％，而MIBK高达1.7wt％。正是由于MIBK法的这些缺点，限制了其工业应用。
目前使用二异丁基酮(DIBK)作为萃取剂分离锆铪时，均需要使用硫氰酸或其盐，由于硫氰酸或其盐有较高的毒性，在分离过程中不环保。
发明内容
本发明的目的在于提供一种盐酸介质中萃取分离锆和铪的方法，其在分离过程中，不需使用有毒物质，可以实现锆铪分离过程的清洁生产。
本发明的再一目的在于提供一种盐酸介质中萃取分离锆和铪的方法，其可以用于含铪的锆化合物的锆铪分离。
本发明的实施例是这样实现的：
本发明的第一方面：将萃取剂与由锆的化学品、盐酸混合形成的酸性料液混合萃取，萃取分相后所得萃余液与碱混合得氢氧化锆沉淀，含铪的负载有机相用碳酸盐反萃，反萃液与碱混合得氢氧化铪沉淀，焙烧氢氧化锆沉淀以及氢氧化铪沉淀，萃取剂包括DIBK和膦酸类萃取剂(含C-P键)组成的混合物。
优选地，膦酸类萃取剂(含C-P键)选自由Cyanex921、Cyanex923、Cyanex925和Cyanex572组成的组中的至少一种。
优选地，萃取剂在萃取前与盐酸进行预萃取。
优选地，预萃取时的盐酸浓度为1.0-4.0mol/L，和/或，预萃取时，所述萃取剂与盐酸等体积进行。
优选地，酸性料液中还包括无机盐。
本发明的第二方面：将锆的化学品与盐酸混合形成酸性料液，使用萃取剂萃取酸性料液，萃取分相后得萃余液和含铪的负载有机相，萃余液与碱混合得氢氧化锆沉淀，含铪的负载有机相用碳酸盐反萃，反萃液与碱混合得氢氧化铪沉淀，焙烧氢氧化锆沉淀以及氢氧化铪沉淀，萃取剂包括DIBK和膦酸类萃取剂(含C-P键)组成的混合物。
本发明实施例的有益效果包括：DIBK与Cyanex923组成的协萃体系或DIBK和膦酸类萃取剂(含C-P键)组成的协萃体系优先萃取锆铪混合溶液中含量相对较小的铪，因而传 质少，萃取容量大；工艺流程简单、易操作、萃取效率高，并且在这个分离过程中不需要使用如硫氰酸或其盐等高毒性物质，整个分离过程清洁。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将对本发明实施例中的技术方案进行清楚、完整地描述。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
下面对本发明的锆和铪的分离方法进行具体说明。
锆铪在自然界中总是共生的。一般市售的锆化学品中铪含量(m Hf/m (Zr+Hf))较少(一般为1％～3％)，对其进行分离时如果采用优先萃取铪的萃取剂将有较大的优势。因“镧系收缩”，锆和铪的原子半径、离子半径基本相同，物理化学性质非常相似，彼此分离十分困难，被认为是元素周期表中最难分离的元素之一。但由于锆和铪具有相异的核性能，锆对热中子吸收截面小，被广泛用做核反应堆包壳和结构材料，核级锆中要求铪含量小于0.01％，而铪具有大的热中子吸收截面，主要用作核反应的中子控制棒，核级铪中要求锆含量小于2％。因此，锆铪分离是获得核级锆铪材料的关键。
作为本发明的一个方面，本发明提供一种盐酸介质中萃取分离锆和铪的方法，主要用于实现锆和铪的高效分离，其包括以下步骤：
在本发明中的溶剂萃取法分离锆铪的体系中影响锆铪分离的因素很多，它们是：萃取剂的体积百分含量；料液中锆铪的浓度、硫酸盐的浓度、氯离子浓度、总游离酸酸度和反萃取时碳酸盐的摩尔浓度等。为了提高分离效果，在本发明的一些实施方式中，对制得的酸性料液中的各成分浓度进行控制，例如：
如果料液中锆离子和铪离子的总浓度低于0.05mol/L，虽然有利于锆铪的分离，但料液处理量较大，消耗总酸量大。如果料液中锆离子和铪离子的总浓度高于2.0mol/L，当总游离酸酸度小于0.05mol/L，锆铪易水解，分离效率差；当总游离酸酸度大于4.0mol/L，锆铪分离系数降低。为了保证锆铪较高的分离效果，料液中锆离子和铪离子的总浓度在0.05-2.0mol/L为佳；优选为0.5-1.5mol/L，更优选为1.0-1.5mol/L。
料液的总游离酸酸度为0.5-4.0mol/L，优选为1.0-2.5mol/L。
同时，优选地，酸性料液中，氯离子浓度优选控制为0.5-5.0mol/L，可选地，酸性料液中还可以引入无机盐，当酸性料液中在加入硫酸盐作为无机盐时，还可以引入硫酸根离子，硫酸根离子浓度优选控制为0～1.25mol/L，例如硫酸根离子浓度为0.2mol/L、0.4mol/L、0.5mol/L、0.6mol/L、0.8mol/L、1.0mol/L和1.25mol/L等。
可选地，酸性料液还可以加入氨水等用于调节酸性料液中的pH值。
使用萃取剂萃取已制得的酸性料液，其中，萃取剂包括DIBK和DIBK和膦酸类萃取剂(含C-P键)形成的协萃体系，膦酸类萃取剂选自由Cyanex921、Cyanex923、Cyanex925和Cyanex572组成的组中的至少一种，即可以使用DIBK和Cyanex921形成的协萃体系，也可以使用DIBK和Cyanex923形成的协萃体系，也可以使用DIBK和Cyanex925形成的协萃体系，也可以使用DIBK和Cyanex572形成的协萃体系，在本发明的一些实施方式中，还可以使用DIBK与Cyanex921、Cyanex923、Cyanex925以及Cyanex572共同形成的协萃体系，与使用单一萃取剂的液-液萃取相比，协同萃取更加高效。
其中，二异丁基酮(DIBK)是一种中性含氧类萃取剂，DIBK的闪点为47℃，水溶度为0.043wt％，水溶性极低。
在本发明的一些实施方式中，萃取剂中，使用DIBK和膦酸类萃取剂(含C-P键)形成的协萃体系时，膦酸类萃取剂(含C-P键)的体积含量均优选为2％～40％，更优选为2％～20％。还需说明的是，在协萃体系中，还可以使用与Cyanex921或Cyanex923或Cyanex925或Cyanex572性质相似的萃取剂替代Cyanex921或Cyanex923或Cyanex925或Cyanex572，也可以进一步添加具有相似性质的其他萃取剂。
膦酸类萃取剂(含C-P键)是一种有机氧化膦类萃取剂，当其他因素固定，随着膦酸类萃取剂(含C-P键)体积百分比的增大，其锆铪分离系数β值先增加后减小，若膦酸类萃取剂(含C-P键)体积百分比浓度大于40％，对锆的萃取量太大，不利于锆铪的分离，所以其含量为2-20％为佳。
萃取时，可以采用单级或者多级(例如4～20级)共流和/或逆液方式进行，两相混合时间为2～30分钟，优选为5～15分钟，萃取槽的槽内温度优选控制在0～40℃之间，例如5℃、10℃、15℃、20℃、25℃、30℃和35℃等。
已报道的MIBK体系、DIBK-TBP体系、DIBK-P204体系、DIBK-P350体系、DIBK-TOPO体系对锆铪的萃取机理研究表明，在SCN -存在时，SCN -均直接参与萃合物的组成。根据路易斯软硬酸碱理论，Hf 4+与Zr 4+均为硬酸，但Hf 4+酸性要强于Zr 4+酸性，更易与硬碱类萃取剂形成较稳定的配合物。而膦酸类萃取剂(含C-P键)比磷酸类萃取剂(含C-O-P键)的路易斯碱性更强，更易与离子半径小的Hf 4+形成较稳定的萃合物，亦即其易于被萃取。利用空间位阻大的DIBK所具有的强选择性，与膦酸类萃取剂(含C-P键)组成协萃体系，优先萃取铪，可以显著提高其对铪的萃取率和锆铪的分离效率。
在本发明的一些实施方式中，萃取剂可以预先与稀释剂混合稀释，稀释剂可以选自磺化煤油、己烷、异辛烷和200#溶剂油等，应当理解，稀释剂可以由上述物质的一种或至少两种组成。
将萃取剂与盐酸混合进行预萃取，其中，盐酸浓度优选为1.0-4.0mol/L，例如可以是 1.0mol/L，1.5mol/L，2.0mol/L，2.5mol/L，3.0mol/L，3.5mol/L，4.0mol/L等。预萃取的作用是使萃取剂达到预饱和状态。在预萃取时，优选萃取剂和盐酸等体积进行。
萃取剂进行预萃取后作为有机相，酸性料液作为水相，混合进行萃取，萃取分相后，锆留在萃余水相中，得到无铪或少铪的锆溶液，水相中的铪进入有机相，得到含铪的负载有机相。
对得到的无铪的锆溶液，用碱(例如氨水、烧碱等)进行沉淀，得氢氧化锆沉淀。
对含铪的负载有机相，用碳酸盐进行反萃，可选地，碳酸盐可以是碳酸钠、碳酸钾、碳酸镁和碳酸铝等，反萃时，碳酸盐可以是上述物质中的一种或者至少两种的混合物。反萃后，铪进入水相，得到的反萃液即为富铪溶液。得到的富铪溶液中，m Hf/m (Hf+Zr)的重量比为10％～40％。其中，用于反萃的碳酸盐浓度例如可以是0.05-5.0mol/L。
然后用碱(例如氨水、烧碱等)对富铪溶液进行沉淀，得到氢氧化铪沉淀。
用去离子水对得到的氢氧化锆沉淀和氢氧化铪沉淀进行洗涤，洗涤后的氢氧化锆和氢氧化铪沉淀进行焙烧，优选地，焙烧温度为850-1800℃，例如：经850℃、1000℃、1200℃、1400℃、1600℃和1800℃进行焙烧，焙烧时还可以以梯度升温的方式进行。
焙烧后得到氧化锆为原子能级，含锆的氧化铪经进一步分离后也可达到原子能级。
作为本发明的另一个方面，本发明提供一种盐酸介质中萃取分离锆和铪的方法，主要用于实现锆和铪的高效分离，其与上述的分离方法大致相同，区别在于，酸性料液在萃取前配制得到：
首先，将待分离的含有锆和铪的原料制成酸性料液，即将锆的化学品与、盐酸混合形成酸性料液，优选地，酸性料液中可以加入无机盐，无机盐可以选自由氯化铵、氯化钠、氯化镁、硫酸铵、硫酸钠和硫酸镁组成的组中的至少一种。
在本发明的一些实施方式中，酸性料液也可以加入一定量的氨水用于调节料液中的pH值。
酸性料液例如可以按以下方法制取：
一、锆英石经碳化、氯化或者锆英石直接沸腾氯化制备出四氯化锆，四氯化锆溶解在水中，加入氨水和无机盐配制为酸性料液，其中氨水、无机盐可以定量加入。
二、锆英石经碱熔、水洗后、稀盐酸浸出溶液，加入定量的盐酸和无机盐配制为酸性料液。
三、氧氯化锆直接溶解在水中，加入定量的盐酸和无机盐配制为酸性料液。
四、氧化锆或金属锆或氧化铪或金属铪，或含有其它杂质的锆废料或铪废料的原料按第一种或第二种方法制备料液，加入定量的盐酸和无机盐配制为酸性料液。
由以上方法制得的酸性料液中，料液的组成大致如表1所示：
表1酸性料液的组成
Figure PCTCN2018072336-appb-000001
以下结合实施例对本发明的特征和性能作进一步的详细描述。
实施例1
一种分离锆和铪的方法，具体步骤如下：
(1)配制酸性料液：水相组成为初始锆铪离子总浓度1.5mol/L，其中铪离子浓度约为0.018mol/L，水相酸度为1.7mol/L，(NH 4) 2SO 4浓度为0.8mol/L。
(2)萃取剂采用90％(v/v)的DIBK和10％(v/v)的Cyanex923组成的混合有机相，先将萃取剂与等体积3.5mol/L的盐酸进行预萃取一次，然后将预萃取后的萃取剂作为有机相，酸性料液作为水相，控制相比(有机相∶水相)为2∶1，在室温下对料液进行单级萃取，两相混合时间为10分钟，分相后，锆留在萃余液中，得到少铪的锆溶液，再用氨水沉淀锆溶液，得到氢氧化锆沉淀，而料液中的铪全被萃入有机相，得到含铪的负载有机相；
(3)将负载有机相用1.0mol/L碳酸钾进行反萃，反萃的相比(有机相∶水相)为1∶2，两相混合时间为10分钟，得到含锆的富铪溶液，采用氨水进行沉淀，得到氢氧化铪沉淀；
(4)将氢氧化锆和氢氧化铪沉淀分别用去离子水洗涤，洗涤后的氢氧化锆和氢氧化铪沉淀分别经1200℃焙烧，得到少铪的氧化锆和含锆的氧化铪产品。
萃取前后水相中锆铪金属离子的总浓度用EDTA标准液滴定法测定，酸度采用氢氧化钠标准液滴定法测定，铪的浓度采用ICP-MS法测定，再用差减法分别计算有机相中锆铪金属离子的总浓度和铪离子的浓度，依次计算分配比、分离系数和萃取率。
有机相中金属离子的浓度，锆铪分配比、分离系数及萃取率计算如下：
Figure PCTCN2018072336-appb-000002
Figure PCTCN2018072336-appb-000003
Figure PCTCN2018072336-appb-000004
Figure PCTCN2018072336-appb-000005
Figure PCTCN2018072336-appb-000006
Figure PCTCN2018072336-appb-000007
Figure PCTCN2018072336-appb-000008
式中：[Zr] o、[Hf] o——分别为有机相中锆、铪的浓度，g/L；
[Zr] a、[Hf] a——分别为水相中锆、铪的浓度，g/L；
Figure PCTCN2018072336-appb-000009
——分别为水相中锆、铪离子的初始浓度，g/L；
V a、V o——分别为水相和有机相的体积，mL；
D r(Zr)、D r(Hf)——分别为锆、铪的分配比；
[Zr] ea、[Hf] ea——分别为平衡时水相中锆、铪离子浓度，g/L；
[Zr] eo、[Hf] eo——分别为平衡时有机相中锆、铪离子浓度，g/L；
β——为锆铪的分离系数；
E Zr、E Hf——分别为有机相对锆、铪的萃取率。
通过计算，该体系对铪的萃取率为82.50％，而锆的萃取率为14.50％，锆铪的分离系数达到27。
实施例2
有机相组成为90％(v/v)的DIBK、2％(v/v)的Cyanex921和8％(v/v)的磺化煤油(作为稀释剂)，并预先用等体积3.4mol/L的盐酸预萃取一次，水相组成为初始锆铪离子总浓度1.5mol/L，其中铪离子浓度为0.018mol/L，水相酸度为1.7mol/L，(NH 4) 2SO 4加入量为0.8mol/L，控制相比为2∶1，在室温下进行单级萃取，两相混合时间为5分钟，分相后得到萃余液和含铪的负载有机相，萃余液再用氨水沉淀，得到氢氧化锆沉淀；将负载有机相用1.0mol/L碳酸钾进行反萃，洗涤和反萃的相比均为1∶2，两相混合时间为5分钟，得到含锆的富铪溶液，采用氨水进行沉淀，得到含锆的氢氧化铪沉淀。其它操作步骤同实施例1。
对铪的萃取率为58.98％，锆的萃取率为11.03％，锆铪的分离系数达到10。
实施例3
有机相组成为90％(v/v)的DIBK、8％(v/v)的Cyanex923和2％(v/v)的异辛烷(作为稀释剂)，并预先用等体积4.0mol/L的盐酸预萃取一次，水相组成为初始锆铪离子总浓度1.0mol/L，其中铪离子浓度为0.012mol/L，水相酸度为2.0mol/L，(NH 4) 2SO 4加入量为0.8mol/L，控制相比为2∶1，在室温下进行单级萃取，两相混合时间为5分钟，分相后得到萃余液和含铪的负载有机相，萃余液再用氨水沉淀，得到少铪的氢氧化锆沉淀；将负载有机相用1.0mol/L碳酸钠进行反萃，洗涤和反萃的相比均为1∶2，两相混合时间为5分钟，得到含锆的富铪溶液，采用氨水进行沉淀，得到含锆的氢氧化铪沉淀。其它操作步骤同实施例1。
对铪的萃取率为54.98％，锆的萃取率为14.51％，锆铪的分离系数达到7。
实施例4
有机相组成为60％(v/v)的DIBK和40％(v/v)的Cyanex925，并预先用油水相比为1：3的1.0mol/L盐酸预萃取一次，水相组成为初始锆铪离子总浓度0.5mol/L，其中铪离子浓度为0.006mol/L，水相酸度为1.0mol/L，(NH 4) 2SO 4加入量为0.6mol/L，控制相比为2∶1，在室温下进行单级萃取，两相混合时间为2分钟，分相后得到萃余液和含铪的负载有机相，萃余液再用氢氧化钠沉淀，得到少铪的氢氧化锆沉淀；将负载有机相用3.0mol/L碳酸钾进行反萃，洗涤和反萃的相比均为1∶2，两相混合时间为5分钟，得到含锆的富铪溶液，其中，富铪溶液中，m Hf/m (Hf+Zr)的重量比为10％。采用氢氧化钠进行沉淀，得到含锆的氢氧化铪沉淀。其它操作步骤同实施例1。
对铪的萃取率为64.66％，锆的萃取率为14.21％，锆铪的分离系数达到8。
实施例5
有机相组成为80％(v/v)的DIBK和20％(v/v)的Cyanex923，并预先用等体积2.4mol/L的盐酸预萃取一次，水相组成为初始锆铪离子总浓度1.0mol/L，其中铪离子浓度为0.012mol/L，水相酸度为1.2mol/L，(NH 4) 2SO 4加入量为1.25mol/L，控制相比为2∶1，在室温下进行单级萃取，两相混合时间为30分钟，分相后得到萃余液和含铪的负载有机相，萃余液再用氨水沉淀，得到少铪的氢氧化锆沉淀；将负载有机相用2.0mol/L碳酸镁进行反萃，洗涤和反萃的相比均为1∶2，两相混合时间为5分钟，得到含锆的富铪溶液，其中，富铪溶液中，m Hf/m (Hf+Zr)的重量比为15％。采用氨水进行沉淀，得到含锆的氢氧化铪沉淀。其它操作步骤同实施例1。
对铪的萃取率为68.22％，锆的萃取率为12.25％，锆铪的分离系数达到12。
实施例6
有机相组成为70％(v/v)的DIBK和30％(v/v)的Cyanex923，并预先用等体积4.0mol/L的盐酸预萃取一次，水相组成为初始锆铪离子总浓度2.0mol/L，其中铪离子浓度为0.024mol/L，水相酸度为2.0mol/L，(NH 4) 2SO 4加入量为1.0mol/L，控制相比为2∶1，在室温下进行单级萃取，两相混合时间为25分钟，分相后得到萃余液和含铪的负载有机相，萃余液再用氢氧化钾沉淀，得到少铪的氢氧化锆沉淀；将负载有机相用2.0mol/L碳酸铝进行反萃，洗涤和反萃的相比均为1∶2，两相混合时间为25分钟，得到含锆的富铪溶液，其中，富铪溶液中，m Hf/m (Hf+Zr)的重量比为20％。采用氨水进行沉淀，得到含锆的氢氧化铪沉淀。其它操作步骤同实施例1。
对铪的萃取率为70.78％，锆的萃取率为13.64％，锆铪的分离系数达到15。
实施例7
有机相组成为85％(v/v)的DIBK和15％(v/v)的Cyanex925，并预先用等体积4.0mol/L的盐酸预萃取一次，水相组成为初始锆铪离子总浓度0.5mol/L，其中铪离子浓度为0.006mol/L，水相酸度为2.0mol/L，(NH 4) 2SO 4加入量为0.8mol/L，控制相比为2∶1，在室温下进行单级萃取，两相混合时间为10分钟，分相后得到萃余液和含铪的负载有机相，萃余液再用氨水沉淀，得到少铪的氢氧化锆沉淀；将负载有机相用3.0mol/L碳酸钠进行反萃，洗涤和反萃的相比均为1∶2，两相混合时间为10分钟，得到含锆的富铪溶液，其中，富铪溶液中，m Hf/m (Hf+Zr)的重量比为20％。采用氨水进行沉淀，得到含锆的氢氧化铪沉淀。其它操作步骤同实施例1。
对铪的萃取率为68.42％，锆的萃取率为12.68％，锆铪的分离系数达到16。
实施例8
有机相组成为65％(v/v)的DIBK和35％(v/v)的Cyanex923，并预先用等体积3.4mol/L的盐酸预萃取一次，水相组成为初始锆铪离子总浓度1.2mol/L，其中铪离子浓度为0.015mol/L，水相酸度为1.7mol/L，(NH 4) 2SO 4加入量为0.8mol/L，控制相比为2∶1，在室温下进行单级萃取，两相混合时间为15分钟，分相后得到萃余液和含铪的负载有机相，萃余液再用氨水沉淀，得到少铪的氢氧化锆沉淀；将负载有机相用1.0mol/L碳酸钠进行反萃，洗涤和反萃的相比均为1∶2，两相混合时间为15分钟，得到含锆的富铪溶液，其中，富铪溶液中，m Hf/m (Hf+Zr)的重量比为35％。采用氨水进行沉淀，得到含锆的氢氧化铪沉淀。其 它操作步骤同实施例1。
对铪的萃取率为82.50％，锆的萃取率为14.50％，锆铪的分离系数达到28。
实施例9
有机相组成为90％(v/v)的DIBK和2％(v/v)的Cyanex923以及8％(v/v)的己烷，并预先用等体积2.0mol/L的盐酸预萃取一次，水相组成为初始锆铪离子总浓度1.5mol/L，其中铪离子浓度为0.018mol/L，水相酸度为1.0mol/L，(NH 4) 2SO 4加入量为0.4mol/L，控制相比为2∶1，在室温下进行单级萃取，两相混合时间为5分钟，分相后得到萃余液和含铪的负载有机相，萃余液再用氨水沉淀，得到少铪的氢氧化锆沉淀；将负载有机相用2.0mol/L碳酸钠进行反萃，洗涤和反萃的相比均为1∶2，两相混合时间为5分钟，得到含锆的富铪溶液，采用氨水进行沉淀，得到含锆的氢氧化铪沉淀。其它操作步骤同实施例1。
对铪的萃取率为62.55％，锆的萃取率为11.84％，锆铪的分离系数达到8。
实施例10
有机相组成为90％(v/v)的DIBK和8％(v/v)的Cyanex923以及2％(v/v)的200#溶剂，并预先用等体积4.0mol/L的盐酸预萃取一次，水相组成为初始锆铪离子总浓度2.0mol/L，其中铪离子浓度为0.024mol/L，水相酸度为1.9mol/L，(NH 4) 2SO 4加入量为0.8mol/L，控制相比为2∶1，在室温下进行单级萃取，两相混合时间为10分钟，分相后得到萃余液和含铪的负载有机相，萃余液再用氨水沉淀，得到少铪的氢氧化锆沉淀；将负载有机相用1.5mol/L碳酸钠进行反萃，洗涤和反萃的相比均为1∶2，两相混合时间为10分钟，得到含锆的富铪溶液，采用氨水进行沉淀，得到含锆的氢氧化铪沉淀。其它操作步骤同实施例1。
对铪的萃取率为68.44％，锆的萃取率为12.62％，锆铪的分离系数达到9。
实施例11
有机相组成为90％(v/v)的DIBK和10％(v/v)的Cyanex925，并预先用等体积3.0mol/L的盐酸预萃取一次，水相组成为初始锆铪离子总浓度1.5mol/L，其中铪离子浓度为0.018mol/L，水相酸度为1.5mol/L，(NH 4) 2SO 4加入量为0.4mol/L，控制相比为2∶1，在室温下进行单级萃取，两相混合时间为10分钟，分相后得到萃余液和含铪的负载有机相，萃余液再用氨水沉淀，得到氢氧化锆沉淀；将负载有机相用1.0mol/L碳酸钾进行反萃，洗涤和反萃的相比均为1∶2，两相混合时间为10分钟，得到含锆的富铪溶液，采用氨水进行沉淀，得到含锆的氢氧化铪沉淀。其它操作步骤同实施例1。
对铪的萃取率为58.98％，锆的萃取率为11.03％，锆铪的分离系数达到10。
实施例12
有机相组成为90％(v/v)的DIBK、2％(v/v)的Cyanex572和8％(v/v)的磺化煤油(作为稀释剂)，并预先用等体积2.8mol/L的盐酸预萃取一次，水相组成为初始锆铪离子总浓度1.5mol/L，其中铪离子浓度为0.018mol/L，水相酸度为1.4mol/L，(NH 4) 2SO 4加入量为0.6mol/L，控制相比为2∶1，在室温下进行单级萃取，两相混合时间为5分钟，分相后得到萃余液和含铪的负载有机相，萃余液再用氨水沉淀，得到氢氧化锆沉淀；将负载有机相用1.0mol/L碳酸钾进行反萃，洗涤和反萃的相比均为1∶2，两相混合时间为5分钟，得到含锆的富铪溶液，采用氨水进行沉淀，得到含锆的氢氧化铪沉淀。其它操作步骤同实施例1。
对铪的萃取率为44.81％，锆的萃取率为11.22％，锆铪的分离系数达到7。
实施例13
有机相组成为90％(v/v)的DIBK、8％(v/v)的Cyanex572和2％(v/v)的磺化煤油(作为稀释剂)，并预先用等体积2.8mol/L的盐酸预萃取一次，水相组成为初始锆铪离子总浓度1.5mol/L，其中铪离子浓度为0.018mol/L，水相酸度为1.4mol/L，(NH 4) 2SO 4加入量为0.6mol/L，控制相比为2∶1，在室温下进行单级萃取，两相混合时间为5分钟，分相后得到萃余液和含铪的负载有机相，萃余液再用氨水沉淀，得到少铪的氢氧化锆沉淀；将负载有机相用1.0mol/L碳酸钠进行反萃，洗涤和反萃的相比均为1∶2，两相混合时间为5分钟，得到含锆的富铪溶液，采用氨水进行沉淀，得到含锆的氢氧化铪沉淀。其它操作步骤同实施例1。
对铪的萃取率为50.28％，锆的萃取率为12.64％，锆铪的分离系数达到10。
实施例14
有机相组成为60％(v/v)的DIBK和40％(v/v)的Cyanex572，并预先用等体积的3.0mol/L盐酸预萃取一次，水相组成为初始锆铪离子总浓度0.5mol/L，其中铪离子浓度为0.006mol/L，水相酸度为1.5mol/L，NH 4Cl加入量为0.6mol/L，控制相比为2∶1，在室温下进行单级萃取，两相混合时间为2分钟，分相后得到萃余液和含铪的负载有机相，萃余液再用氢氧化钠沉淀，得到少铪的氢氧化锆沉淀；将负载有机相用3.0mol/L碳酸钾进行反萃，洗涤和反萃的相比均为1∶2，两相混合时间为5分钟，得到含锆的富铪溶液，其中，富铪溶液中，m Hf/m (Hf+Zr)的重量比为13％。采用氢氧化钠进行沉淀，得到含锆的氢氧化铪沉淀。其它操作步骤同实施例1。
对铪的萃取率为52.42％，锆的萃取率为13.22％，锆铪的分离系数达到8。
实施例15
有机相组成为80％(v/v)的DIBK和20％(v/v)的Cyanex923，并预先用等体积3.2mol/L的盐酸预萃取一次，水相组成为初始锆铪离子总浓度1.0mol/L，其中铪离子浓度为0.012mol/L，水相酸度为1.6mol/L，(NH 4) 2SO 4加入量为1.25mol/L，控制相比为2∶1，在室温下进行单级萃取，两相混合时间为30分钟，分相后得到萃余液和含铪的负载有机相，萃余液再用氨水沉淀，得到少铪的氢氧化锆沉淀；将负载有机相用2.0mol/L碳酸镁进行反萃，洗涤和反萃的相比均为1∶2，两相混合时间为5分钟，得到含锆的富铪溶液，其中，富铪溶液中，m Hf/m (Hf+Zr)的重量比为30％。采用氨水进行沉淀，得到含锆的氢氧化铪沉淀。其它操作步骤同实施例1。
对铪的萃取率为70.58％，锆的萃取率为11.53％，锆铪的分离系数达到18。
实施例16
有机相组成为70％(v/v)的DIBK和30％(v/v)的Cyanex921，并预先用等体积4.0mol/L的盐酸预萃取一次，水相组成为初始锆铪离子总浓度2.0mol/L，其中铪离子浓度为0.024mol/L，水相酸度为2.0mol/L，(NH 4) 2SO 4加入量为0.8mol/L，控制相比为2∶1，在室温下进行单级萃取，两相混合时间为25分钟，分相后得到萃余液和含铪的负载有机相，萃余液再用氢氧化钾沉淀，得到少铪的氢氧化锆沉淀；将负载有机相用2.0mol/L碳酸铝进行反萃，洗涤和反萃的相比均为1∶2，两相混合时间为25分钟，得到含锆的富铪溶液，其中，富铪溶液中，m Hf/m (Hf+Zr)的重量比为30％。采用氨水进行沉淀，得到含锆的氢氧化铪沉淀。其它操作步骤同实施例1。
对铪的萃取率为73.06％，锆的萃取率为11.66％，锆铪的分离系数达到18。
实施例17
有机相组成为85％(v/v)的DIBK和15％(v/v)的Cyanex572，并预先用等体积2.8mol/L的盐酸预萃取一次，水相组成为初始锆铪离子总浓度0.05mol/L，其中铪离子浓度为0.0006mol/L，水相酸度为1.4mol/L，(NH 4) 2SO 4加入量为0.8mol/L，控制相比为2∶1，在室温下进行单级萃取，两相混合时间为10分钟，分相后得到萃余液和含铪的负载有机相，萃余液再用氨水沉淀，得到少铪的氢氧化锆沉淀；将负载有机相用3.0mol/L碳酸钠进行反萃，洗涤和反萃的相比均为1∶2，两相混合时间为10分钟，得到含锆的富铪溶液，其中，富铪溶液中，m Hf/m (Hf+Zr)的重量比为15％。采用氨水进行沉淀，得到含锆的氢氧化铪沉淀。其它操作步骤同实施例1。
对铪的萃取率为48.32％，锆的萃取率为11.68％，锆铪的分离系数达到10。
实施例18
有机相组成为65％(v/v)的DIBK和35％(v/v)的Cyanex572，并预先用等体积3.0mol/L的盐酸预萃取一次，水相组成为初始锆铪离子总浓度1.0mol/L，其中铪离子浓度为0.012mol/L，水相酸度为1.5mol/L，MgCl 2加入量为0.4mol/L，控制相比为2∶1，在室温下进行单级萃取，两相混合时间为15分钟，分相后得到萃余液和含铪的负载有机相，萃余液再用氨水沉淀，得到少铪的氢氧化锆沉淀；将负载有机相用1.5mol/L碳酸钠进行反萃，洗涤和反萃的相比均为1∶2，两相混合时间为15分钟，得到含锆的富铪溶液，其中，富铪溶液中，m Hf/m (Hf+Zr)的重量比为13％。采用氨水进行沉淀，得到含锆的氢氧化铪沉淀。其它操作步骤同实施例1。
对铪的萃取率为48.48％，锆的萃取率为12.24％，锆铪的分离系数达到8。
实施例19
有机相组成为90％(v/v)的DIBK和8％(v/v)的Cyanex923以及2％(v/v)的Cyanex923，并预先用等体积3.6mol/L的盐酸预萃取一次，水相组成为初始锆铪离子总浓度1.5mol/L，其中铪离子浓度为0.018mol/L，水相酸度为1.8mol/L，(NH 4) 2SO 4加入量为0.8mol/L，控制相比为2∶1，在室温下进行单级萃取，两相混合时间为5分钟，分相后得到萃余液和含铪的负载有机相，萃余液再用氨水沉淀，得到少铪的氢氧化锆沉淀；将负载有机相用2.5mol/L碳酸钠进行反萃，洗涤和反萃的相比均为1∶2，两相混合时间为5分钟，得到含锆的富铪溶液，采用氨水进行沉淀，得到含锆的氢氧化铪沉淀。其它操作步骤同实施例1。
对铪的萃取率为82.48％，锆的萃取率为10.20％，锆铪的分离系数达到36。
实施例20
有机相组成为90％(v/v)的DIBK和8％(v/v)的Cyanex572以及2％(v/v)的异辛烷，并预先用等体积2.8mol/L的盐酸预萃取一次，水相组成为初始锆铪离子总浓度2.0mol/L，其中铪离子浓度为0.024mol/L，水相酸度为1.4mol/L，NaCl加入量为0.8mol/L，控制相比为2∶1，在室温下进行单级萃取，两相混合时间为10分钟，分相后得到萃余液和含铪的负载有机相，萃余液再用氨水沉淀，得到少铪的氢氧化锆沉淀；将负载有机相用1.5mol/L碳酸钠进行反萃，洗涤和反萃的相比均为1∶2，两相混合时间为10分钟，得到含锆的富铪溶液，采用氨水进行沉淀，得到含锆的氢氧化铪沉淀。其它操作步骤同实施例1。
对铪的萃取率为45.22％，锆的萃取率为10.48％，锆铪的分离系数达到9。
实施例21
本实施例与实施例1的区别在于，选用的协萃体系不同，本实施例中，选用的协萃体系采用90％(v/v)的DIBK、5％(v/v)的Cyanex923以及5％(v/v)的Cyanex572，其他原料配比、制备方法等均相同。
以上所描述的实施例是本发明一部分实施例，而不是全部的实施例。本发明的实施例的详细描述并非旨在限制要求保护的本发明的范围，而是仅仅表示本发明的选定实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。

Claims (10)

  1. 一种盐酸介质中萃取分离锆和铪的方法，其特征在于，包括以下步骤：
    将萃取剂与由锆的化学品、盐酸混合形成的酸性料液混合萃取，萃取分相后所得萃余液与碱混合得氢氧化锆沉淀，含铪的负载有机相用碳酸盐反萃，反萃液与碱混合得氢氧化铪沉淀，焙烧所述氢氧化锆沉淀以及所述氢氧化铪沉淀，所述萃取剂包括DIBK和膦酸类萃取剂组成的混合物；
    优选地，膦酸类萃取剂选自由Cyanex921、Cyanex923、Cyanex925和Cyanex572组成的组中的至少一种；
    优选地，萃取剂在萃取前与盐酸进行预萃取；
    优选地，预萃取时的盐酸浓度为1.0-4.0mol/L，和/或，预萃取时，所述萃取剂与盐酸等体积进行；
    优选地，酸性料液中还包括无机盐。
  2. 根据权利要求1所述的盐酸介质中萃取分离锆和铪的方法，其特征在于，所述酸性料液中，总游离酸酸度为0.5-4.0mol/L，优选为1.0-2.5mol/L；
    和/或，所述酸性料液中，锆离子和铪离子的总浓度为0.05-2.0mol/L，优选为0.5-1.5mol/L，更优选为1.0-1.5mol/L。
  3. 根据权利要求2所述的盐酸介质中萃取分离锆和铪的方法，其特征在于，所述酸性料液中，氯离子的浓度为0.5-5.0mol/L，优选为2.0-4.0mol/L；
    和/或，硫酸根离子的浓度为0-1.25mol/L。
  4. 根据权利要求1所述的盐酸介质中萃取分离锆和铪的方法，其特征在于，所述无机盐选自由氯化铵、氯化钠、氯化镁、硫酸铵和硫酸钠组成的组中的至少一种。
  5. 根据权利要求1所述的盐酸介质中萃取分离锆和铪的方法，其特征在于，所述萃取剂中，膦酸类萃取剂的体积分数为2vt％-40vt％，优选为2vt％-20vt％；
    和/或，所述反萃液中，m Hf/m (Hf+Zr)的重量比为10％～40％。
  6. 根据权利要求5所述的盐酸介质中萃取分离锆和铪的方法，其特征在于，萃取前，将所述萃取剂与稀释剂混合，优选地，所述稀释剂选自由磺化煤油、己烷、异辛烷和200#溶剂油组成的组中的至少一种。
  7. 根据权利要求1-6任一项所述的盐酸介质中萃取分离锆和铪的方法，其特征在于，萃取采用单级或多级共流和/或逆液方式进行，优选地，两相混合时间为2-30min，更优选为5-15min；优选地，萃取时萃取槽的槽内温度为0-40℃。
  8. 根据权利要求1-6任一项所述的盐酸介质中萃取分离锆和铪的方法，其特征在 于，所述碳酸盐选自由碳酸钠、碳酸钾、碳酸镁和碳酸铝组成的组的中的至少一种。
  9. 根据权利要求1-6任一项所述的盐酸介质中萃取分离锆和铪的方法，其特征在于，焙烧在850-1800℃条件下进行，和/或，焙烧前，对所述氢氧化锆沉淀和所述氢氧化铪沉淀进行洗涤。
  10. 一种盐酸介质中萃取分离锆和铪的方法，其特征在于，将锆的化学品与盐酸混合形成酸性料液，
    使用萃取剂萃取所述酸性料液，萃取分相后得萃余液和含铪的负载有机相，萃余液与碱混合得氢氧化锆沉淀，含铪的负载有机相用碳酸盐反萃，反萃液与碱混合得氢氧化铪沉淀，焙烧所述氢氧化锆沉淀以及所述氢氧化铪沉淀，所述萃取剂包括DIBK和膦酸类萃取剂组成的混合物。
PCT/CN2018/072336 2018-01-03 2018-01-12 盐酸介质中萃取分离锆和铪的方法 WO2019134184A1 (zh)

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