Ruthenium(III) chloride is also known as ruthenium chloride. RuCl3=207.43, reddish brown or black leaf-shaped crystals, easy to deliquesce. The relative density is 3.11, and it decomposes into elemental substances when the temperature is higher than 500℃. Insoluble in cold water and carbon disulfide, decomposes when exposed to hot water, insoluble in ethanol, and soluble in hydrochloric acid. It reacts with potassium iodide solution to form an iodide precipitate. When hydrogen sulfide is introduced into the solution, the precipitate becomes ruthenium trisulfide, which can form corresponding ammonia, cyanide, and nitroso compounds with complexing agents such as ammonia, potassium cyanide, and potassium nitrite. The complex is reduced to blue divalent ruthenium ions by reaction with sodium amalgam or titanium trichloride. It can be obtained by directly combining ruthenium metal with chlorine at high temperatures, or by adding hydrochloric acid to ruthenium hydroxide, followed by evaporation, concentration, and crystallization. Used for the determination of sulfite, the manufacture of chlororuthenate, and as electrode coating materials.
Method 1, a production process of Ruthenium(III) chloride, including the following steps:
Step (1), produce RuO4 gas according to the traditional method; then use dilute hydrochloric acid to absorb the RuO4 gas until the concentration of Ru in the solution is 59g/L. At the same time, adjust the pH to 1.9 to obtain a ruthenium-containing solution;
The dilute hydrochloric acid is a mixture of hydrochloric acid with a mass fraction of 37% and water in a volume ratio of 1.9:1;
Step (2): Add a dispersing solvent to the ruthenium-containing solution obtained in step (1). The volume of the dispersing solvent added is 9.8% of the volume of the ruthenium-containing solution to obtain a dispersed ruthenium-containing solution;
The dispersion solvent is a mixture of hydrogen peroxide, ethanol and acetone, and the volume ratio of hydrogen peroxide, ethanol and acetone in the dispersion solvent is 1:7.9:0.95;
Step (3), spray drying:
The dispersed ruthenium-containing solution obtained in step (2) is spray-dried using a spray dryer to obtain Ruthenium(III) chloride powder; the spray-drying temperature is 180-200°C, and the feed amount is 800-1000mL/ h; The nozzle of the spray dryer is made of polytetrafluoroethylene. The nozzle diameter of the spray dryer is 0.5mm.
Method 2: Put 10 grams of ruthenium powder into reactor 2, add 5N hydrochloric acid to absorption bottle 4-9, and add 10% sodium hydroxide solution to absorption bottle 10-11. First check whether the entire system is normal: reactor 2, empty bottle 3, absorption bottle 4-11, buffer bottle 12, vacuum pump 13. Then start the vacuum pump 13, close the vent valve 14, check whether each absorption bottle is bubbled, and adjust the vacuum to 100mmHg.
Add 500 ml of sodium hypochlorite solution into reactor 2, start heating with electric furnace 1, and keep the temperature of the reactor at 50°C. The solution in the reactor will turn brown and black. After 30 minutes of reaction, slowly add 9N H2SO4 solution to the reaction In vessel 2 (added from the bottom), the color of the solution becomes lighter, accompanied by the escape of a large amount of golden RuO4 gas. At this time, stop adding H2SO4. After the RuO4 evaporates, add sodium hypochlorite solution. The color of the solution becomes darker until the color is no longer When it reaches a deeper level, stop adding sodium hypochlorite solution, then heat to maintain the temperature in the reactor at 50°C, react for 10 minutes, then add 9N H2SO4 solution, and repeat until the solution becomes colorless and transparent. The reactor temperature was raised to 70°C and maintained for 2 hours to drive out the dissolved RuO4 gas, and the solution became colorless and transparent. RuO4 gas is absorbed by the hydrochloric acid in the absorption bottle to generate brown-red Ruthenium(III) chloride. The sodium hydroxide in the absorption bottle 10-11 absorbs the waste gas and waste acid in the reaction system. After the reaction is completed, slowly open the vent valve 14. Stop the vacuum pump 13 and suck out the reaction residue. After testing, the yield can reach 95.8%.
Ruthenium(III) chloride (RuCl3) is widely used in the preparation of metal anode ruthenium coatings, the preparation of hydrogenation catalysts, and the production of computer hard disk memory materials. Therefore, a large amount of ruthenium-containing materials are produced in the above production processes. Secondary resource waste.
A method for recovering Ruthenium(III) chloride in ruthenium plating waste liquid, the method includes:
S1-1: Accurately transfer 30ml of waste ruthenium plating solution into a three-necked flask, slowly add 8ml of sulfuric acid and m1=0.8gKMnO4 in sequence, heat in a water bath at T1=75°C for t=1h, oxidize and distill the RuO4 and evaporated Remaining liquid;
S1-2: Absorb RuO4 gas with n=6mol/L HCl solution to generate RuCl3 hydrochloric acid solution;
S1-3: Distill under reduced pressure at 55°C for 8 hours to obtain β-RuCl3·xH2O crystals;
S2-1: Filter the obtained residual liquid, discard the filter residue, and obtain the filtrate;
S2-2: Add NaOH solution to the filtrate to adjust the pH to alkaline, add 5 ml of pre-oxidant 10% NaClO and 1g NaCl, and incubate in a water bath at 80°C for 30 minutes to obtain the pre-oxidized raffinate;
S2-3: Use sulfonated kerosene as diluent and n-octanol as demulsifier to prepare N503 with a concentration of X% = 30%. Mix and shake the prepared N503 with an equal volume of HCl solution with a concentration of 3mol/L. 3 times, until the acidity of the water phase remains unchanged, take out the organic phase, which is the prepared amine extractant; mix the amine extractant with the preoxidized raffinate volume ratio Y = 1 Mix the raffinate, add it to the separatory funnel, shake for 15 minutes, leave to separate, remove the water phase, and retain the organic phase, which is the extraction phase;
S2-4: Add a NaOH solution with a concentration of 2 mol/L to the extraction phase prepared in S2-3. The volume ratio of the extraction phase to the NaOH solution is 1. Shake for 15 to 30 minutes. Leave to separate and separate. Take out The water phase is the stripping phase;
S3: Add the stripping phase obtained in step S2-4 to step S1-1 for oxidative distillation.
After detection and calculation, the β-RuCl3·xH2O crystal content obtained in this method is 38.8% (theoretical value is 35%~38%), the distillation yield is 85.3%, and the extraction rate is 80.4%. The total The recovery rate is 91.5%.
[1] Dictionary of Chemical Substances
[2]CN201610759891.8 A production process of Ruthenium(III) chloride
[3][Chinese invention] CN201910743605.2 A method for recovering Ruthenium(III) chloride in ruthenium plating waste liquid
[4][Chinese invention] CN200710303681.9 A preparation method of Ruthenium(III) chloride
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