CN115679124B - Process for separating hafnium and zirconium - Google Patents
Process for separating hafnium and zirconium Download PDFInfo
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- CN115679124B CN115679124B CN202211383243.9A CN202211383243A CN115679124B CN 115679124 B CN115679124 B CN 115679124B CN 202211383243 A CN202211383243 A CN 202211383243A CN 115679124 B CN115679124 B CN 115679124B
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- activated carbon
- hafnium oxide
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Abstract
The invention provides a process for separating hafnium and zirconium, and relates to the technical field of hydrometallurgy. The process for separating hafnium and zirconium comprises the following steps: crushing raw materials, and pre-absorbing; step three, preparing active carbon microcapsules; and step four, preparing a pre-extraction solution. The nano hafnium oxide is carried by nitrogen to be absorbed under the action of the activated carbon and the activated carbon microcapsule, and then the obtained activated carbon absorbing the nano hafnium oxide is remapped into the activated carbon microcapsule, so that the nano hafnium oxide is utilized to the maximum extent, and the obtained activated carbon microcapsule is safer than the hafnium oxide.
Description
Technical Field
The invention relates to the technical field of hydrometallurgy, in particular to a process for separating hafnium and zirconium.
Background
In nature, hafnium is often co-produced with zirconium, and zirconium-containing minerals all contain hafnium, which is similar to zirconium in quality and mainly occurs in zirconite. The amount of HfO2 contained in the zircon used in industry is 0.5-2%. Beryllium zircon in secondary zirconium ores can contain HfO2 up to 15%. Also, a modified zircon Qu Jingdan contains more than 5% HfO 2. The latter two minerals have low reserves and have not been used industrially. Hafnium is mainly recovered from the zirconium production process.
The disclosed patent CN202110304657.7 specifically relates to a method for preparing high-purity hafnium oxide by separating zirconium and hafnium through solvent extraction, which comprises the following steps: the raw material adopts hafnium oxide to prepare extraction precursor solution with the concentration of 50-80 g/L of hafnium oxide, the extraction precursor solution is subjected to first-stage extraction treatment, and the first extractant adopts 5-10% of N235. In the preparation of the pre-extraction liquid, hafnium oxide is taken as a raw material, and the pre-extraction liquid is obtained by digestion with concentrated sulfuric acid, water immersion and filtration in sequence; however, since hafnium oxide itself has a major irritating effect, for example on the skin: skin and mucous membrane irritation, above the eye: the influence of stimulus, and thus the preparation of the involved precursor solution is limited, and only a few protection means are needed, so that the health of workers is affected due to a little carelessness.
Disclosure of Invention
(one) solving the technical problems
Aiming at the defects of the prior art, the invention provides a process for separating hafnium and zirconium, which solves the problem that the worker has to use a protection means to perform solvent extraction to separate zirconium and hafnium to prepare high-purity hafnium oxide due to the stimulation of the hafnium oxide on the worker.
(II) technical scheme
In order to achieve the above purpose, the invention is realized by the following technical scheme: a process for separating hafnium and zirconium comprising the steps of:
step one: crushing of raw materials
Crushing and grinding hafnium oxide raw materials in vacuum at the temperature range of 0-5 ℃ to obtain nano hafnium oxide;
step two: pre-absorption
Blowing the nano hafnium oxide to the activated carbon by using nitrogen, absorbing the nano hafnium oxide under the action of the activated carbon, and further absorbing the nano hafnium oxide by using an activated carbon microcapsule at the rear side of the activated carbon adsorption layer;
step three: preparation of active carbon microcapsule
Drying the activated carbon absorbing nano hafnium oxide at 50 ℃, and preparing activated carbon microcapsules from the dried activated carbon absorbing nano hafnium oxide and collodion;
step four: preparation of Pre-extraction liquid
The active carbon microcapsule is taken as a raw material, and is digested by concentrated sulfuric acid, immersed in water and filtered to obtain a pre-extraction liquid.
Preferably, the activated carbon is coconut shell activated carbon and petroleum activated carbon according to the following weight ratio of 10:1, wherein the distribution thickness ratio of the activated carbon to the activated carbon microcapsule is 3:1.
preferably, the activated carbon microcapsules have a diameter of less than 50 μm and are stored at ambient temperature in an environment having an air humidity of less than 25%.
Preferably, the preparation of the pre-extraction liquor is carried out by pumping the reaction gas into the gypsum slurry for absorption.
(III) beneficial effects
The present invention provides a process for separating hafnium and zirconium. The beneficial effects are as follows:
according to the invention, the nano hafnium oxide carried by nitrogen is absorbed through the actions of the activated carbon and the activated carbon microcapsule, and then the obtained activated carbon absorbing the nano hafnium oxide is remapped into the activated carbon microcapsule, so that the nano hafnium oxide is utilized to the maximum extent, and the obtained activated carbon microcapsule is safer than the hafnium oxide.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Embodiment one:
a process for separating hafnium and zirconium comprising the steps of:
step one: crushing of raw materials
Crushing and grinding hafnium oxide raw materials in vacuum at the temperature range of 0-5 ℃ to obtain nano hafnium oxide;
step two: pre-absorption
The nitrogen is used for carrying nano hafnium oxide and blowing the nano hafnium oxide to the activated carbon, the nano hafnium oxide is absorbed under the action of the activated carbon, and the nano hafnium oxide is further absorbed by using activated carbon microcapsules at the rear side of an activated carbon adsorption layer, wherein the activated carbon is coconut shell activated carbon and petroleum activated carbon according to the following ratio of 10:1, the distribution thickness ratio of the activated carbon to the activated carbon microcapsule is 3:1, a step of;
step three: preparation of active carbon microcapsule
Drying the activated carbon absorbing nano hafnium oxide at 50 ℃, and then preparing the dried activated carbon absorbing nano hafnium oxide and collodion into activated carbon microcapsules, wherein the diameter of the activated carbon microcapsules is smaller than 50 mu m, and the activated carbon microcapsules are stored in an environment with air humidity smaller than 25% at normal temperature when not used;
step four: preparation of Pre-extraction liquid
Taking an active carbon microcapsule as a raw material, sequentially carrying out digestion by concentrated sulfuric acid, water immersion and filtration to obtain a pre-extraction liquid, and pumping reaction gas into gypsum slurry for absorption when preparing the pre-extraction liquid, namely absorbing generated carbon dioxide by the gypsum slurry;
step five: preparation of the first extractant
The fuel is prepared by mixing N235, octanol and kerosene, and the volume percentage of each component is as follows: n2355-10%, octanol 5-10% and kerosene 80-90%;
step six: first stage extraction:
mixing the pre-extraction liquid with a first extractant, performing multistage cross-flow extraction, separating zirconium and hafnium in the pre-extraction liquid to obtain low-zirconium raffinate and a first-stage loaded organic phase, and performing back extraction and regeneration on the first-stage loaded organic phase by taking the low-zirconium raffinate as a second-stage pre-extraction liquid; adding hydrochloric acid solution into the first section of loaded organic phase, and carrying out multistage countercurrent back extraction to obtain back extraction liquid and a first section of lean organic phase, wherein sulfuric acid after neutralization of the back extraction liquid is dissolved to be used as extraction precursor liquid; adding sodium carbonate solution into the first-stage lean organic phase, performing multistage countercurrent regeneration to obtain regenerated liquid and regenerated organic phase, pumping the regenerated liquid into a sewage workshop for advanced treatment, and pumping the regenerated organic phase into the first-stage extraction for recycling;
step seven: preparation of the second extractant
The fuel is prepared by mixing N235, octanol and kerosene, and the volume percentage of each component is as follows: 20-40% of N235, 15-20% of octanol and 40-65% of kerosene;
step eight: second stage extraction
Mixing the low-zirconium raffinate with a second extractant, performing multistage countercurrent extraction, separating other impurities in the low-zirconium raffinate to obtain a second-stage raffinate and a loaded organic phase, performing neutralization treatment on the second-stage raffinate, and performing back extraction and regeneration on the second-stage loaded organic phase; adding hydrochloric acid solution into the second section loaded organic phase, and carrying out multistage countercurrent back extraction to obtain low-zirconium back extraction liquid and a second section lean organic phase; adding sodium carbonate solution into the second-stage lean organic phase, performing multistage countercurrent regeneration to obtain regenerated liquid and regenerated organic phase, pumping the regenerated liquid into a sewage workshop for advanced treatment, and pumping the regenerated organic phase into the second-stage extraction for recycling;
step nine: post-treatment: precipitating the low-zirconium strip liquor by ammonia water, washing, drying and calcining to obtain high-purity hafnium oxide; the H+ concentration in the hafnium sulfate feed liquid is 5-7 mol/L, and the concentration of hafnium oxide is 61-66 g/L; the oil-water ratio of the extraction in the first stage extraction is 3-5:1, the extraction stage number is 15-20, and the mixing time of the organic phase and the raffinate is 10-20 min; the oil-water ratio of extraction in the second stage extraction is 3-5:1, the extraction stage number is 10-15, and the mixing time of the organic phase and the low-zirconium raffinate is 10-20 min; the oil-water ratio of back extraction in the second stage extraction is 10-15:1, the back extraction stage number is 4-6, and the mixing time of the organic phase and the hydrochloric acid is 15-30 min; the concentration of hydrochloric acid in the back extraction liquid in the first-stage extraction and the second-stage extraction is controlled to be 4-6 mol/L.
The oil-water ratio of back extraction in the first stage extraction is 5-10:1, the back extraction stage number is 2-4, and the mixing time of the organic phase and the hydrochloric acid is 15-30 min.3. The method for preparing high-purity hafnium oxide by separating zirconium and hafnium by solvent extraction according to claim 1, wherein: the oil-water ratio of regeneration in the first-stage extraction and the second-stage extraction is 3-5:1, the regeneration stage number is 2-4, and the mixing time of the organic phase and sodium carbonate is 10-30 min.
The concentration of the regenerated liquid sodium carbonate in the first-stage extraction and the second-stage extraction is controlled to be 80-120 g/L.
The zirconium impurity content of the high-purity low-zirconium hafnium oxide product is less than 0.02 percent.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (4)
1. A process for separating hafnium and zirconium, characterized by; the method comprises the following steps:
step one: crushing of raw materials
Crushing and grinding hafnium oxide raw materials in vacuum at the temperature range of 0-5 ℃ to obtain nano hafnium oxide;
step two: pre-absorption
Blowing the nano hafnium oxide to the activated carbon by using nitrogen, absorbing the nano hafnium oxide under the action of the activated carbon, and further absorbing the nano hafnium oxide by using an activated carbon microcapsule at the rear side of the activated carbon adsorption layer;
step three: preparation of active carbon microcapsule
Drying the activated carbon absorbing nano hafnium oxide at 50 ℃, and preparing activated carbon microcapsules from the dried activated carbon absorbing nano hafnium oxide and collodion;
step four: preparation of Pre-extraction liquid
The active carbon microcapsule is taken as a raw material, and is digested by concentrated sulfuric acid, immersed in water and filtered to obtain a pre-extraction liquid.
2. The process for separating hafnium and zirconium according to claim 1, wherein: the activated carbon is coconut shell activated carbon and petroleum activated carbon according to the following weight ratio of 10:1, wherein the distribution thickness ratio of the activated carbon to the activated carbon microcapsule is 3:1.
3. the process for separating hafnium and zirconium according to claim 1, wherein: the diameter of the activated carbon microcapsule is less than 50 mu m, and the activated carbon microcapsule is preserved in an environment with the air humidity of less than 25% at normal temperature.
4. The process for separating hafnium and zirconium according to claim 1, wherein: the preparation of the pre-extraction liquid uses pumping of the reaction gas into the gypsum slurry for absorption.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1057912A (en) * | 1951-12-13 | 1954-03-11 | Sylvester And Company | Improvements in the recovery of zirconia from its ores |
| SE9102818D0 (en) * | 1990-10-12 | 1991-09-27 | Westinghouse Electric Corp | A METHOD OF PURIFYING ZIRCONIUM TETRACHLORIDE AND HAFNIUM TETRACHLORIDE IN A VAPOR STREAM |
| JP2008115063A (en) * | 2006-11-06 | 2008-05-22 | Mitsuhide Kawasaki | High purity hafnium material and method of manufacturing the material by using solvent extraction method |
| CN102021335A (en) * | 2009-09-16 | 2011-04-20 | 北京有色金属研究总院 | Method for separating zirconium from hafnium by using elution extraction method |
| CA2834151A1 (en) * | 2011-05-04 | 2012-11-08 | Orbite Aluminae Inc. | Processes for recovering rare earth elements from various ores |
| CN106435221A (en) * | 2016-10-10 | 2017-02-22 | 郭爽 | Method for preparing nuclear-grade sponge zirconium and nuclear-grade sponge hafnium |
| CN106521190A (en) * | 2016-11-17 | 2017-03-22 | 中国科学院长春应用化学研究所 | Purpose and method of amido-contained neutral phosphine extracting agent for extracting and separating zirconium and/or hafnium |
-
2022
- 2022-11-07 CN CN202211383243.9A patent/CN115679124B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1057912A (en) * | 1951-12-13 | 1954-03-11 | Sylvester And Company | Improvements in the recovery of zirconia from its ores |
| SE9102818D0 (en) * | 1990-10-12 | 1991-09-27 | Westinghouse Electric Corp | A METHOD OF PURIFYING ZIRCONIUM TETRACHLORIDE AND HAFNIUM TETRACHLORIDE IN A VAPOR STREAM |
| JP2008115063A (en) * | 2006-11-06 | 2008-05-22 | Mitsuhide Kawasaki | High purity hafnium material and method of manufacturing the material by using solvent extraction method |
| CN102021335A (en) * | 2009-09-16 | 2011-04-20 | 北京有色金属研究总院 | Method for separating zirconium from hafnium by using elution extraction method |
| CA2834151A1 (en) * | 2011-05-04 | 2012-11-08 | Orbite Aluminae Inc. | Processes for recovering rare earth elements from various ores |
| CN106435221A (en) * | 2016-10-10 | 2017-02-22 | 郭爽 | Method for preparing nuclear-grade sponge zirconium and nuclear-grade sponge hafnium |
| CN106521190A (en) * | 2016-11-17 | 2017-03-22 | 中国科学院长春应用化学研究所 | Purpose and method of amido-contained neutral phosphine extracting agent for extracting and separating zirconium and/or hafnium |
Non-Patent Citations (1)
| Title |
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| 真空技术及应用系列讲座第五讲：气体捕集式真空泵;徐成海;真空(05);全文 * |
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