CN1111204C

CN1111204C - Preparation of high-purity chloro-osmate solution

Info

Publication number: CN1111204C
Application number: CN99115143A
Authority: CN
Inventors: 陆跃华; 董旭玲; 周杨霁
Original assignee: Sino Platinum Metals Co Ltd
Current assignee: Sino Platinum Metals Co Ltd
Priority date: 1999-09-17
Filing date: 1999-09-17
Publication date: 2003-06-11
Anticipated expiration: 2019-09-17
Also published as: CN1288964A

Abstract

The present invention relates to a preparation method of chlorine osmate solution with high purity, which comprises the steps: adding coarse sodium osmate or coarse osmium powder in a sulphuric acid medium to distil osmium after an oxidizing agent is added in the medium, absorbing osmium tetroxide by alkali solution, converting the osmium tetroxide into a mixing reagent of chlorine osmate, wveitel and salicylaldoxime, and removing the trace quantity of base metal with extraction; then, 99.99 % chlorine osmate solution with high purity is prepared.

Description

A kind of solution manufacturing method of high-purity chloro-osmate

A kind of solution manufacturing method of high-purity chloro-osmate.The present invention belongs to precious metals metallurgy.

Osmium is one of platinum family element, and osmium has stronger catalytic activity, or a kind of nutritive substance in the body redox processes.Along with science and technology development, the exploitation of novel material, in recent years, high-purity osmium and compound thereof more and more are used to fields such as Aeronautics and Astronautics, microelectronics, biomedicine.For example: high-purity osmium powder product can be done electron source in the aviation electronics device, adds the O that is made by high-purity osmium powder on a small quantity in the plant growth-promoting agent _sO ₄But, Promoting plant growth.Yet the preparation of high-purity osmium powder is difficulty relatively.The chemical valence of metal osmium and compound thereof changes more, and O is arranged _s(III), O _s(IV), Os (VI), Os (VII), O _sO ₄(VIII) equivalent state, the easy oxidation of osmium generates stable oxide O _sO ₄, 40.6～40.7 ℃ of this oxide fusing points, 134 ℃ of boiling points, as easy as rolling off a log volatilization, volatile matter has strong impulse and toxicity to human body, these character make purity be 99.99% and the preparation difficulty of above high-purity osmium powder bigger.A technology " novel process of separating the purification osmium from the osmium absorption liquid "＜CSTAD is arranged, project year numbers: 92210294) adopt distillation osmium one alkali lye to absorb the Technology that a hydrazine hydrate reduction is settled out osmium oxide compound one calcining hydrogen reduction one osmium powder, produce the osmium powder between the purity 99.00-99.98%, do not reach the requirement of purity 99.99%, mainly be trace copper in the osmium powder, iron, nickel content between 0.002～0.005%, do not reach requirement less than 0.001%.

The objective of the invention is to improve the preparation method of osmium powder or its compound, remove micro-copper base metal, iron, nickel impurity in thick osmium powder or its compound, make its purity can reach 99.99% requirement.

The solution manufacturing method of a kind of high-purity chloro-osmate of inventing, comprise distillation osmium, alkali liquor absorption osmium, be converted into chloro-osmate, extract and separate base metal, be prepared into the several steps of high-purity chloro-osmate of purity 99.99%, the concrete steps of its feature are: 1. be that thick sodium osmic acid or the thick osmium powder of 90%-99% is that raw material distills in following condition with grade, make osmium change O into _sO ₄Gas distills out: starve to thick that to add concentration in sour sodium or the thick osmium powder be the sulfuric acid solution of 3mol/L, the sodium chlorate solution who adds a small amount of concentration again and be 10% weight ratio makees oxidant, in about 100 ℃ distillations of temperature; 2. be that the aqueous slkali of weight ratio NaOH 20%+ ethanol 0.5% absorbs the O that 1 step distills out with concentration _sO ₄Gas, absorption liquid slowly are warming up to about temperature 50 C and heated 2-3 hour, obtain more stable sodium osmic acid solution, and osmium concentration is about 20g/L in the solution, and the content of copper, iron, nickel is 0.02～0.022g/L; 3. with 2 step gained sodium osmic acid solution, at temperature 50-70 ℃, add HCl neutralization and hydrolysis, add a small amount of hydrazine hydrate, precipitate reduction goes out O _sO ₂, O _sO ₂Precipitation is the HCl dissolving of 6mol/L with concentration, after the filtration, and evaporate to dryness solution, adjusting acidity with HCl is about 0.001mol/L～4mol/L, this moment, osmium was converted into the chloro-osmate state; 4. the mix reagent chloroformic solution that replaces nabam and salicylaldoxime to form with diethyl extracts the 3 step gained chloro-osmate aqueous solution, remove copper, iron, nickel, extraction conditions is: diethyl is for mol ratio=1 of nabam and salicylaldoxime in the mix reagent: 0.1～1: 3, mol ratio=24 of mix reagent and copper+iron+nickel: 1～10: 1, the volume ratio of water and organic phase=0.5～2: 1, extraction acidity 0.01mol/L～4mol/L, 3～5 grades of extraction progression, every grade of 2min～8min of extraction time.The optimum extraction condition of the 4th step is: mix reagent compares=19: 1 with the mol of copper+iron+nickel, and the volume ratio of water and organic phase=1: 1, extraction acidity are PH=1.5,3 grades of extraction progression, extraction time 6min.

The advantage of the solution manufacturing method of the high-purity chloro-osmate of inventing is: 1, only with last 2 steps change of original technology, the 3rd step precipitate reduction goes out O _sO ₂After added and changed the osmium sodium chloride operation into, the 4th step is improved to extraction copper removal, iron, nickel, namely reaches to obtain the purpose that purity is high-purity osmium sodium chloride salt of 99.99%, can be connected preferably with prior art.2, method is comparatively easy, executes possible, comparatively reliable.

Embodiment:

The 1st step: be that 95% thick osmium powder 331.6g makes raw material with grade, place the glass cucurbit, to wherein adding the sulfuric acid solution that concentration is 3mol/L, the sodium chlorate solution who adds a small amount of concentration again and be 10% weight ratio makees oxidant, in about 100 ℃ distillations of temperature, make osmium become O _sO ₄Gas distills out; The 2nd step: be that the aqueous slkali of weight ratio NaOH20%+ ethanol 0.5% absorbs with concentration, absorption liquid slowly is warming up to about temperature 50 C and heated 2.5 hours, obtain more stable sodium osmic acid solution, starving concentration in the solution is 21g/L, copper concentration is 0.022g/l, nickel concentration is 0.02g/L, and concentration of iron is 0.02g/L, overall solution volume 15L; The 3rd step: 2 step gained sodium osmic acid solution are about 60 ℃ in temperature, add HCl neutralization and hydrolysis, add a small amount of hydrazine hydrate reduction and are settled out O _sO ₂, O _sO ₂Precipitation is dissolved with the HCl of concentration 6mol/L, after the filtration, and evaporate to dryness solution, adjusting acidity with HCL is about PH=1.5, this moment, osmium was converted into the osmium sodium chloride state; The 4th step: the mix reagent chloroformic solution that replaces nabam and salicylaldoxime to form with diethyl extracts 3 step gained osmium sodium chloride solution, remove trace copper, iron, nickel, its condition is: diethyl is for mol ratio=1 of nabam and salicylaldoxime in the mix reagent: 0.1～1: 3, mol ratio=24 of mix reagent and copper+iron+nickel: 1～10: 1, the volume ratio of water and organic phase=0.5～2: 1, extraction acidity is about PH=1.5,3～5 grades of extraction progression, every grade of 2min～8min of extraction time, be divided into 6 parts of solution extractions, it the results are shown in following table: extraction yield 1 0.022＜0.0001＞99.54% 0.020＜0.0001＞99.50 0.011 0.00012 99.43%2 0.022 0.00018 99.18% 0.020＜0.0001＞99.50 0.021 0.00047 97.76%3 0.022 0.00018 99.18% 0.020＜0.0001＞99.50 0.021＜0.0001＞99.52%4 0.022＜0.0001＞99.54% 0.020＜0.0001＞99.50 0.021＜0.0001＞99.52%5 0.022 0.00017 99.23% 0.020＜0.0001＞99.50 0.021＜0.0001＞99.52%6 0.022＜0.0001＞99.54% 0.020＜0.0001＞99.50 0.021＜0.0001＞99.52% osmium was not extracted after extraction yield stoste extracted after the extraction yield stoste extraction after volume Cu (g/L) Ni (g/L) Fe (g/L) number stoste extraction.

The effect of invention: in the test-results table by impurity such as Fe, Cu, Ni in the listed extracting and separating osmium sodium chloride of the embodiment solution, the percentage extraction of copper, iron, nickel is all about 99% as can be seen, concentration drops to less than between 0.0001g/L～0.00047g/L from about 0.02g/L, copper, iron, the nickel content in osmium sodium chloride is less than 0.0004%, and osmium is not extracted, and has obtained the solution of the osmium sodium chloride of purity 99.99%.

Claims

1, a kind of solution manufacturing method of high-purity chloro-osmate, method comprise that the distillation osmium is O _sO ₄, alkali lye is received osmium, is converted into chloro-osmate, extract and separate base metal, is prepared into the several steps of solution of high-purity chloro-osmate of purity 99.99%, it is characterized in that:

1.1, be that 90%～99% thick sodium osmic acid or thick osmium powder distill in following condition with grade, make osmium change O _sO ₄Gas distills out; Adding concentration in thick sodium osmic acid or the thick osmium powder is the sulfuric acid solution of 3mol/L, and the sodium chlorate solution who adds a small amount of concentration again and be 10% weight ratio makees oxidant, in about 100 ℃ distillations of temperature;

1.2, the O that distills out of 1 step _sO ₄Gas concentration is that the aqueous slkali of weight ratio NaOH20%+ ethanol 0.5% absorbs, and absorption liquid slowly is warming up to and heats 2～3 hours about temperature 50 C, obtains more stable sodium osmic acid solution, osmium concentration is about 20g/L in the solution, copper, iron, the content of nickel respectively are 0.02～0.022g/L;

1.3, with 2 step gained sodium osmic acid solution, 50～70 ℃ of temperature, add HCI neutralization and hydrolysis, add a small amount of hydrazine hydrate, precipitate reduction goes out O _sO ₂, O _sO ₂Precipitation is the HCl dissolving of 6mol/L with concentration, evaporate to dryness solution after filtering, and adjusting acidity with HCI is about 0.001mol/L～4mol/L, this moment, osmium was converted into the chloro-osmate state;

1.4, the mix reagent chloroformic solution formed for nabam and salicylaldoxime with diethyl extracts the 3 step gained chloro-osmate aqueous solution, remove copper, iron, nickel, extraction conditions is: diethyl is for the mol ratio=1: 0.1～1: 3 of nabam with salicylaldoxime in the mix reagent, mix reagent compares=24: 1～10: 1 with the mol of copper+iron+nickel, the volume ratio of water and organic phase=0.5～2: 1, extraction acidity 0.01mol/L～4mol/L, extraction progression 3-5 level, extraction time every grade of 2min～8min.

2, the solution manufacturing method of a kind of high-purity chloro-osmate as claimed in claim 1, the condition that it is characterized in that step 4 is: mix reagent compares=19: 1 with the mol of copper+iron+nickel, the volume ratio of water and organic phase=1: 1, extraction acidity is PH=1.5,3 grades of extraction progression, extraction time 6min.