Technical field
The present invention relates to a kind of method for preparing ruthenium trichloride.
Background technology
Ruthenium trichloride is a kind of important inorganics, can generate multiple complex compound with many reagent reacts, it also is the initiator of the many ruthenium complexs of preparation, it can also be as catalyst for reaction such as many organic polymerizations, isomerization, hydrogenation, ruthenium trichloride can also be used for the mensuration of sulphite, the manufacturing of ruthenium hydrochloride salt, is used as electrode coating material etc.
The purposes of ruthenium trichloride is very extensive, but the open Preparation of ruthenium trichloride method of document is seldom arranged.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of novel method for preparing ruthenium trichloride, the ruthenium trichloride yield rate height that this method makes, and technology is simple.
For solving the problems of the technologies described above, the invention provides a kind of Preparation of ruthenium trichloride method, comprise the steps:
A is with ruthenium powder and sodium hypochlorite reaction, and solution is brownish black;
B adds sulfuric acid in the solution that step a generates, reaction generates golden yellow RuO 4Gas;
The RuO that c generates step b 4Gas feeds in the hydrochloric acid soln, and reaction generates ruthenium trichloride.
Above-mentioned preparation method, wherein, repeating step a and b are water white transparency until solution.
Above-mentioned preparation method, wherein, with the ruthenium trichloride evaporative crystallization that step c generates, vaporization temperature is 90～100 ℃, mainly obtain β type ruthenium trichloride this moment, if vaporization temperature is higher than 100 ℃, will obtain more α type ruthenium trichloride.
Above-mentioned preparation method, wherein, the temperature of reaction of described step a is 50～70 ℃.
Above-mentioned preparation method, wherein, the temperature of reaction of described step b is 50～70 ℃.
Above-mentioned preparation method, wherein, vitriolic concentration is 8～10N among the described step b.
Above-mentioned preparation method, wherein, among the described step b, when generating a large amount of golden yellow RuO 4During gas, stop to add sulfuric acid.
Above-mentioned preparation method, wherein, described concentration of hydrochloric acid is 5～7N.
Above-mentioned preparation method wherein, adds ethanol in described hydrochloric acid, preferred, based on hydrochloric acid and alcoholic acid weight, alcohol concn is 0.5%～1%, is absorbing RuO 4The hydrochloric acid absorption liquid in add C 2H 5OH is because C 2H 5OH has the reducing property inhibited oxidation to reach the reductive purpose.
Above-mentioned preparation method wherein, behind the described step c, also comprises the alkali lye absorption step, and used alkali lye is the sodium hydroxide of 10%～15% weight, is used for neutralization and absorbs spent acid, waste gas.
Above-mentioned preparation method, wherein, the vacuum tightness of reaction system is 80～130mmHg.
Above-mentioned preparation method wherein, between described step b and c, also comprises step b ', the solution that heating steps b obtains, and Heating temperature is 70～100 ℃, drives dissolved RuO out of 4Gas.
The present invention utilizes clorox to make oxygenant, and the metal Ru powder is oxidized to ruthenic acid sodium.Use the sulfuric acid adjustment of acidity again, make ruthenic acid sodium further be oxidized to xanchromatic ruthenium tetrachloride gas.Absorb with hydrochloric acid at last, make ruthenium tetrachloride be reduced to the ruthenium trichloride of reddish-brown.
Its reaction formula is:
Ru+3NaC10+2NaOH＝Na 2RuO 4+3NaCl+H 2O
Na 2RuO 4+NaClO+H 2SO 4＝RuO 4+Na 2SO 4+NaCl+H 2SO 4
Preparation of ruthenium trichloride method provided by the invention, preparation technology is simple, can effectively prepare ruthenium trichloride, the yield rate height, yield can reach more than 95%.
Description of drawings
Fig. 1 is the preparation method's of preferred embodiment of the present invention schema.
Embodiment
Describe the present invention in detail below in conjunction with embodiment.
Embodiment 1
Get 10 gram ruthenium powder and drop in the reactor 2, add the hydrochloric acid of 5N among the absorption bottle 4-9, add 10% weight sodium hydroxide solution among the absorption bottle 10-11.Check earlier whether total system is normal: reactor 2, empty bottle 3, absorption bottle 4-11, surge flask 12, vacuum pump 13.Start vacuum pump 13 then, close blow-off valve 14, check whether bubbling of each absorption bottle, regulate vacuum tightness and reach 100mmHg.
Add 500 milliliters of chlorine bleach liquores in reactor 2, begin heating with electric furnace 1, keeping the temperature of reactor is 50 ℃, and solution is brownish black in the reactor, reacts after 30 minutes, slowly adds the H of 9N 2SO 4Solution (adds from the bottom) in reactor 2, and solution colour shoals, and with a large amount of golden yellow RuO 4Gas evolution stops to add H this moment 2SO 4, treat RuO 4Add the chlorine bleach liquor after steaming again, solution colour deepens, and when color no longer changes dark, stops to add the chlorine bleach liquor, and 50 ℃ of reactor temperatures are kept in heating then, react 10 minutes, add the H of 9N again 2SO 4Solution is water white transparency to solution so repeatedly.Temperature of reactor is risen to 70 ℃ and kept 2 hours, to drive dissolved RuO out of 4Gas, solution is water white transparency.RuO 4Generate henna ruthenium trichloride after the hydrochloric acid of gas in absorption bottle absorbs, waste gas, spent acid in the sodium hydroxide absorption reaction system among the absorption bottle 10-11 after reaction is finished, are slowly opened blow-off valve 14, stop vacuum pump 13, the sucking-off reaction residue.
After testing, yield can reach 95.8%.
Embodiment 2
Get 8 gram ruthenium powder and drop in the reactor 2, add the hydrochloric acid of 6N and the ethanol (based on hydrochloric acid and alcoholic acid gross weight) of 0.5% weight among the absorption bottle 4-9, add 15% weight sodium hydroxide solution among the absorption bottle 10-11.Check earlier whether total system is normal: reactor 2, empty bottle 3, absorption bottle 4-11, surge flask 12, vacuum pump 13.Start vacuum pump 13 then, close blow-off valve 14, check whether bubbling of each absorption bottle, regulate vacuum tightness and reach 80mmHg.
Add 600 milliliters of chlorine bleach liquores in reactor 2, begin heating with electric furnace 1, keeping the temperature of reactor is 60 ℃, and solution is brownish black in the reactor, reacts after 40 minutes, slowly adds the H of 8N 2SO 4Solution (adds from the bottom) in reactor 2, and solution colour shoals, and with a large amount of golden yellow RuO 4Gas evolution stops to add H this moment 2SO 4, treat RuO 4Add the chlorine bleach liquor after steaming again, solution colour deepens, and when color no longer changes dark, stops to add the chlorine bleach liquor, and 60 ℃ of reactor temperatures are kept in heating then, react 15 minutes, add the H of 8N again 2SO 4Solution is water white transparency to solution so repeatedly.Temperature of reactor is risen to 80 ℃ and kept 2 hours, to drive dissolved RuO out of 4Gas, solution is water white transparency.RuO 4Gas generates henna ruthenium trichloride after absorption bottle absorbs, waste gas, spent acid in the sodium hydroxide absorption reaction system among the absorption bottle 10-11 after reaction is finished, are slowly opened blow-off valve 14, stop vacuum pump 13, the sucking-off reaction residue.
After testing, yield can reach 96.5%.
Embodiment 3
Get 12 gram ruthenium powder and drop in the reactor 2, add the hydrochloric acid of 7N and the ethanol (based on hydrochloric acid and alcoholic acid gross weight) of 1.0% weight among the absorption bottle 4-9, add the sodium hydroxide solution of 12% weight among the absorption bottle 10-11.Check earlier whether total system is normal: reactor 2, empty bottle 3, absorption bottle 4-11, surge flask 12, vacuum pump 13.Start vacuum pump 13 then, close blow-off valve 14, check whether bubbling of each absorption bottle, regulate vacuum tightness and reach 130mmHg.
Add 1000 milliliters of chlorine bleach liquores in reactor 2, begin heating with electric furnace 1, keeping the temperature of reactor is 70 ℃, and solution is brownish black in the reactor, reacts after 50 minutes, slowly adds the H of 10N 2SO 4Solution (adds from the bottom) in reactor 2, and solution colour shoals, and with a large amount of golden yellow RuO 4Gas evolution stops to add H this moment 2SO 4, treat RuO 4Add the chlorine bleach liquor after steaming again, solution colour deepens, and when color no longer changes dark, stops to add the chlorine bleach liquor, and 60 ℃ of reactor temperatures are kept in heating then, react 15 minutes, add the H of 10N again 2SO 4Solution is water white transparency to solution so repeatedly.Temperature of reactor is risen to 100 ℃ and kept 1 hour, to drive dissolved RuO out of 4Gas, solution is water white transparency.RuO 4Gas generates henna ruthenium trichloride after absorption bottle absorbs, waste gas, spent acid in the sodium hydroxide absorption reaction system among the absorption bottle 10-11 after reaction is finished, are slowly opened blow-off valve 14, stop vacuum pump 13, the sucking-off reaction residue.
After testing, yield can reach 96.2%.
The evaporative crystallization of embodiment 4 ruthenium trichlorides
The hydrochloric acid soln of the liquid ruthenium trichloride that the foregoing description is obtained uses conventional methods evaporative crystallization, and vaporization temperature is 90～100 ℃, obtains the crystal water RuCl of ruthenium trichloride 3XH 2O, RuCl 3XH 2Contain the ruthenium amount in the O crystallization and be not less than 36%, the RuCl that obtains 3XH 2O crystallization solubility property is good, contains α type RuCl 3Seldom.
With hydrochloric acid needed concentration is dissolved in its crystallization as required at last.
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