A method for preparing ruthenium trichloride

Abstract

The application provides a preparation method of ruthenium trichloride, and the preparation method comprises the following steps: (1) mixing waste ruthenium aluminum oxide catalyst and porous manganese dioxide catalyst, the specific surface area of the porous manganese dioxide catalyst is not less than 80 m 2 / g, the average particle size is 1-5 μm, and the mass ratio of the catalyst to the waste ruthenium aluminum oxide catalyst is (1-5):100; (2) placing the mixture in a vertical pyrolysis furnace with a mechanical stirring device, roasting the mixture under a CO2 atmosphere at 620-650 ℃ for 2-3.5 hours, and the stirring speed is 300-500 rpm; (3) cooling after the roasting is completed, carrying out hydrochloric acid leaching, solid-liquid separation, alkali melting, water immersion, acidification and oxidative distillation, and obtaining a ruthenium trichloride solution.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of catalyst recovery in petroleum industry, and particularly relates to a preparation method of ruthenium trichloride. BACKGROUND

[0002] With the development of petroleum and chemical industry, the consumption of ruthenium-based catalysts increases year by year, and the production of ruthenium-containing catalysts also increases. It has great industrial application value to recover ruthenium in waste ruthenium catalysts in the form of ruthenium chloride. Ruthenium chloride has a wide application in basic chemical industry and pharmaceutical chemical industry, and at the same time, it can realize efficient recovery and utilization of ruthenium in waste catalysts, which not only helps to alleviate the shortage of precious metal resources, but also reduces the production cost of enterprises, and has important economic and environmental significance. SUMMARY

[0003] In order to solve the above technical problems, the present application provides a preparation method of ruthenium trichloride, which comprises the following steps: (1) mixing waste ruthenium alumina catalyst with porous manganese dioxide catalyst, the specific surface area of the porous manganese dioxide catalyst is not less than 80 m 2 / g, the average particle size is 1-5 μm, and the mass ratio of the catalyst to the waste ruthenium alumina catalyst is (1-5):100; (2) placing the mixture in a vertical pyrolysis furnace with a mechanical stirring device, calcining at 620-650℃ for 2-3.5 hours under CO2 atmosphere, and the stirring speed is 300-500 rpm; (3) cooling after calcination, carrying out hydrochloric acid leaching, solid-liquid separation, alkali fusion, water immersion, acidification and oxidative distillation, and obtaining a ruthenium trichloride solution.

[0004] The present method effectively improves the removal efficiency of carbon deposition in waste ruthenium alumina catalyst by the cooperation of porous manganese dioxide catalyst and carbon dioxide atmosphere, and reduces the loss of ruthenium element. The particle size of the porous manganese dioxide is similar to the pore size of the catalyst, which can enter the internal pores of the catalyst under high-speed stirring, and can help to physically strip and rub the deep carbon deposition, which is helpful to the desorption and decomposition of the carbon deposition. As a catalyst, manganese dioxide can promote the reaction between carbon dioxide and carbon deposition, so that the carbon deposition is converted into carbon monoxide gas and discharged from the system at a lower temperature. The carbon dioxide atmosphere not only provides reactants for carbon deposition removal, but also effectively inhibits the oxidation and volatilization of ruthenium element, preventing the loss of ruthenium element at high temperature. High-speed stirring ensures the uniform distribution of the manganese dioxide catalyst between the catalyst particles, enhances the contact efficiency of the catalyst and the carbon deposition, and also promotes the flow and uniformity of the reaction of the gas in the bed. After calcination, the manganese dioxide catalyst and the catalyst can be efficiently separated by solid-liquid separation, realizing the recovery and recycling of the catalyst, and avoiding the influence of the catalyst on the subsequent process.

[0005] Further, the porous manganese dioxide catalyst is prepared by a sol-gel method. This method helps to obtain a porous manganese dioxide with uniform structure and high specific surface area, thereby improving the catalytic activity and dispersibility of the catalyst.

[0006] Specifically, the specific surface area of the porous manganese dioxide catalyst is 90-120 m 2 / g. This further enhances the contact interface between the catalyst and the carbon deposit, thereby improving the carbon deposit removal efficiency.

[0007] Further, the solid-liquid separation uses a filter screen with a pore size of 10-50 pm. A suitable filter pore size helps to efficiently separate the porous manganese dioxide catalyst from the catalyst, thereby improving the catalyst recovery rate.

[0008] Further, the alkali fusion step includes mixing the catalyst after hydrochloric acid leaching with Na2O2 and NaOH, and alkali fusion at 600-700°C for 1.5-3 hours. This condition helps to completely decompose the residual impurities and promote the conversion of ruthenium.

[0009] Specifically, the mass ratio of Na2O2 to NaOH is 1:0.75-1:1. A reasonable alkali ratio helps to control the alkalinity and fluidity of the reaction system, thereby improving the conversion efficiency of ruthenium.

[0010] Further, the acidification step includes adding sulfuric acid with a mass fraction of 40-98% to the water leaching filtrate of the alkali fusion product, and heating to 90-100°C. This step helps to fully acidify the system, creating favorable conditions for subsequent oxidative distillation.

[0011] Further, the oxidative distillation step includes adding NaClO3 to the acidified liquid to oxidize Ru to RuO4, and absorbing it with hydrochloric acid with a mass fraction of 30-37% to obtain a ruthenium trichloride solution. This step can efficiently convert ruthenium into soluble ruthenium trichloride, facilitating subsequent purification and utilization.

[0012] Further, the stirring speed in the calcination step is 350-450 rpm. A higher stirring speed helps to fully mix the catalyst with the catalyst particles and efficiently strip the carbon deposit.

[0013] Further, the mass ratio of the porous manganese dioxide catalyst to the waste ruthenium alumina catalyst is 1:30 to 1:40. This ratio helps to reduce the catalyst dosage while ensuring synergistic catalytic effect, thereby improving the economy. BRIEF DESCRIPTION OF DRAWINGS

[0014] Figure 1 The flowchart of the method for preparing ruthenium trichloride according to the present application. DETAILED DESCRIPTION

[0015] For the purposes of the present application, a more complete description of which will follow, the present application can be implemented in any numerous ways, including the embodiments described herein. Rather, the embodiments are presented for purposes of illustration and description, and are not intended to limit the scope of the application.

[0016] Furthermore, the terms "first", "second", etc. are used herein only to describe different instances, and do not imply or suggest relative importance or a number of the technical features indicated. Thus, the features defined with "first", "second" can include at least one of the features explicitly or implicitly. In the description of the application, the meaning of "plurality" is at least two, such as two, three, etc., unless otherwise specifically limited. In the description of the application, the meaning of "several" is at least one, such as one, two, etc., unless otherwise specifically limited.

[0017] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description of the application herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0018] In the present application, the technical features described in an open manner include both the closed technical solutions consisting of the listed features and the open technical solutions containing the listed features.

[0019] In the present application, with respect to the numerical range, unless otherwise specified, the numerical range is considered to be continuous and includes the minimum value and the maximum value of the range, as well as every value between the minimum value and the maximum value. Further, when the range is an integer, every integer between the minimum value and the maximum value of the range is included. In addition, when multiple ranges are provided to describe a feature or a characteristic, the ranges can be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all sub-ranges subsumed therein.

[0020] In the present application, with respect to the percentage content, unless otherwise specified, it refers to mass percentage for solid-liquid mixing and solid-solid mixing, and volume percentage for liquid-liquid mixing.

[0021] In the present application, with respect to the percentage concentration, unless otherwise specified, it refers to the final concentration. The final concentration refers to the proportion of the added ingredient in the system after the ingredient is added.

[0022] In the present application, with respect to the temperature parameter, unless otherwise specified, it allows both constant temperature treatment and treatment within a certain temperature range. The constant temperature treatment allows the temperature to fluctuate within the accuracy range controlled by the instrument.

[0023] The "particles" referred to in the present application, or the substance defining the particle size distribution, are not necessarily spherical in shape, but can also be irregular, and can be primary particles or secondary particles. The particle size of the irregular particles is measured as the average of the largest and smallest diameters.

[0024] Example 1: This example provides a method for preparing ruthenium trichloride.

[0025] Petroleum chemical waste ruthenium-alumina catalyst 20 kg (from a hydrogenation unit of a certain petrochemical enterprise, appearance is gray-black cylindrical particles, ruthenium content is about 0.5 wt%, carbon content is about 8 wt%). Particle size 2-10 mm, dried to constant weight. Porous manganese dioxide catalyst 0.5 kg, average particle size 3 μm, specific surface area 90 m 2 / g, prepared by sol-gel method, the specific method is as follows: potassium permanganate is dissolved in deionized water, sodium citrate is added as complexing agent, the pH is adjusted to 7-8, 60°C water bath stirring for 2 hours, the obtained sol is dried at 120°C for 12 hours, the dried material is calcined at 400°C in air for 4 hours, ground through 100 mesh sieve, to get porous manganese dioxide powder with average particle size of 3 μm and specific surface area of 90 m 2 / g.

[0026] The mixture is transferred to a vertical pyrolysis furnace, the furnace body is pre-inflated with CO2 gas (purity 99.99%, flow rate 3000 L / h) for 30 minutes to replace air. Start the stirring device, set the rotation speed to 400 rpm. The heating rate is 10°C / min, and the temperature is raised to 650°C and kept constant for 3 hours, during which CO2 gas is continuously introduced, and the positive pressure in the furnace is maintained (0.02 MPa).

[0027] After the calcination is completed, the heating is stopped, and the natural cooling is carried out to room temperature, and the stirring and CO2 aeration are continued until the temperature is reduced to below 100°C. After cooling, the cooled calcination product is transferred to a 500 L polypropylene stirring tank, 60 L of 30% hydrochloric acid is added for leaching, stirring at 95°C for 2 hours, pressure filtration, then 300 L of deionized water is added, high-speed stirring for 20 min, ultrasonic treatment for 10 min (power 1 kW, frequency 40 kHz), filtration (filter screen aperture 20 μm), separation of porous manganese dioxide catalyst (existing in liquid phase) and catalyst particles (filtrate).

[0028] The residue was mixed with 20 kg of Na2O2 and NaOH (mass ratio 1:0.75), and placed in an electric furnace for alkali fusion at 650°C for 2.5 hours. The alkali fusion product was added to 100 L of deionized water, stirred at 95°C for 3 hours, filtered, and the filtrate was collected. The filtrate was acidified with 98% sulfuric acid to pH = 1, heated to 95°C, and 10 wt% NaClO3 was added dropwise until the solution turned yellow. The stirring was continued for 30 minutes, and the generated RuO4 gas was absorbed with 36% hydrochloric acid to obtain a ruthenium trichloride solution.

[0029] Example 2: The present example provides a method for preparing ruthenium trichloride.

[0030] Petroleum chemical waste ruthenium alumina catalyst 20 kg (from a hydrogenation device of a certain petrochemical enterprise, appearance is gray-black cylindrical particles, ruthenium content is about 0.5 wt%, carbon content is about 8 wt%). The particle size was 2-10 mm, and the mixture was dried to constant weight. Porous manganese dioxide catalyst 0.5 kg, average particle size 1.5 μm, specific surface area 120 m 2 / g, prepared by sol-gel method. The specific method is as follows: potassium permanganate is dissolved in deionized water, sodium citrate is added as a complexing agent, the pH is adjusted to 7-8, and the obtained sol is dried at 120°C for 12 hours. The dried material is calcined in air at 400°C for 4 hours, ground through a 100 mesh sieve, and the porous manganese dioxide powder with an average particle size of 1.5 μm and a specific surface area of 120 m 2 / g is obtained.

[0031] The mixture was transferred to a vertical pyrolysis furnace, and CO2 gas (purity 99.99%, flow rate 3000 L / h) was pre-injected into the furnace for 30 minutes to replace air. The stirring device was started, and the rotation speed was set to 400 rpm. The heating rate was 10°C / min, and the temperature was raised to 650°C and kept constant for 2.5 hours. During this period, CO2 gas was continuously injected, and the pressure in the furnace was kept at 0.02 MPa.

[0032] After the calcination was completed, the heating was stopped, and the temperature was naturally cooled to room temperature. The stirring and CO2 injection were continued until the temperature dropped below 100°C. After cooling, the calcined product was transferred to a 500 L polypropylene stirring tank, 60 L of 30% hydrochloric acid was added for leaching, and the mixture was stirred at 95°C for 2 hours. After pressure filtration, 300 L of deionized water was added, and the mixture was stirred at high speed for 20 min, treated with ultrasonic waves for 10 min (power 1 kW, frequency 40 kHz), and filtered (filter screen aperture 20 μm). The porous manganese dioxide catalyst (present in the liquid phase) and the catalyst particles (residue) were separated.

[0033] The residue was mixed with 20 kg of Na2O2 and NaOH (mass ratio 1:0.75), and placed in an electric furnace for alkali fusion at 650°C for 2.5 hours. The alkali fusion product was added to 100 L of deionized water, stirred at 95°C for 3 hours, filtered, and the filtrate was collected. The filtrate was acidified with 98% sulfuric acid to pH = 1, heated to 95°C, and 10 wt% NaClO3 was added dropwise until the solution turned yellow. Stirring was continued for 30 minutes, and the generated RuO4 gas was absorbed with 36% hydrochloric acid to obtain a ruthenium trichloride solution.

[0034] Example 3: The present example provides a method for preparing ruthenium trichloride.

[0035] Petroleum chemical waste ruthenium alumina catalyst 20 kg (from a hydrogenation device of a certain petrochemical enterprise, appearance is gray-black cylindrical particles, ruthenium content is about 0.5 wt%, carbon content is about 8 wt%). The particle size was 2-10 mm, and the catalyst was dried to constant weight. Porous manganese dioxide catalyst 0.5 kg, average particle size 3 μm, specific surface area 90 m 2 / g, prepared by sol-gel method. The specific method is as follows: potassium permanganate is dissolved in deionized water, sodium citrate is added as a complexing agent, the pH is adjusted to 7-8, and the obtained sol is dried at 120°C for 12 hours. The dried material is calcined in air at 400°C for 4 hours, ground through a 100 mesh sieve, and the porous manganese dioxide powder with an average particle size of 3 μm and a specific surface area of 90 m 2 / g is obtained.

[0036] The mixture was transferred to a vertical pyrolysis furnace, and CO2 gas (purity 99.99%, flow rate 3000 L / h) was introduced into the furnace body for 30 minutes to replace the air. The stirring device was started, and the rotation speed was set to 500 rpm. The heating rate was 10°C / min, and the temperature was raised to 620°C and kept constant for 3 hours. During this period, CO2 gas was continuously introduced, and the pressure in the furnace was kept positive (0.02 MPa).

[0037] After the calcination was completed, the heating was stopped, and the temperature was naturally cooled to room temperature. The stirring and CO2 gas were continued until the temperature dropped below 100°C. After cooling, the calcined product was transferred to a 500 L polypropylene stirring tank, 60 L of 30% hydrochloric acid was added for leaching, and the mixture was stirred at 95°C for 2 hours. Then, 300 L of deionized water was added, and the mixture was stirred at high speed for 20 min and treated with ultrasonic waves for 10 min (power 1 kW, frequency 40 kHz). The mixture was filtered (filter screen aperture 20 μm), and the porous manganese dioxide catalyst (present in the liquid phase) and the catalyst particles (residue) were separated.

[0038] The residue was mixed with 20 kg of Na2O2 and NaOH (mass ratio 1:0.75), and placed in an electric furnace for alkali fusion at 650°C for 2.5 hours. The alkali fusion product was added to 100 L of deionized water, stirred at 95°C for 3 hours, filtered, and the filtrate was collected. The filtrate was acidified with 98% sulfuric acid to pH = 1, heated to 95°C, and 10 wt% NaClO3 was added dropwise until the solution turned yellow. Stirring was continued for 30 minutes, and the generated RuO4 gas was absorbed with 36% hydrochloric acid to obtain a ruthenium trichloride solution.

[0039] Example 4: The present example provides a method for preparing ruthenium trichloride.

[0040] Petroleum chemical waste ruthenium alumina catalyst 20 kg (from a hydrogenation device of a certain petrochemical enterprise, appearance is gray-black cylindrical particles, ruthenium content is about 0.5 wt%, carbon content is about 8 wt%). The particle size was 2-10 mm, and the catalyst was dried to constant weight. 1 kg of porous manganese dioxide catalyst with an average particle size of 3 μm and a specific surface area of 90 m 2 / g was prepared by a sol-gel method. Specifically, potassium permanganate was dissolved in deionized water, sodium citrate was added as a complexing agent, the pH was adjusted to 7-8, and the resulting sol was dried at 120°C for 12 hours. The dried material was calcined in air at 400°C for 4 hours, ground through a 100 mesh sieve, and the porous manganese dioxide powder with an average particle size of 3 μm and a specific surface area of 90 m 2 / g was obtained.

[0041] The mixture was transferred to a vertical pyrolysis furnace, and CO2 gas (purity 99.99%, flow rate 3000 L / h) was introduced into the furnace body for 30 minutes to replace the air. The stirring device was started, and the rotation speed was set to 400 rpm. The temperature was raised at a rate of 10°C / min, and after reaching 650°C, the temperature was kept constant for 2 hours, during which CO2 gas was continuously introduced to maintain a positive pressure (0.02 MPa) in the furnace.

[0042] After the calcination was completed, the heating was stopped, and the temperature was naturally cooled to room temperature. The stirring and CO2 gas flow were continued until the temperature dropped below 100°C. After cooling, the calcined product was transferred to a 500 L polypropylene stirring tank, 60 L of 30% hydrochloric acid was added for leaching, and the mixture was stirred at 95°C for 2 hours. After pressure filtration, 300 L of deionized water was added, and the mixture was stirred at high speed for 20 min, treated with ultrasonic waves for 10 min (power 1 kW, frequency 40 kHz), and filtered (filter screen aperture 20 μm) to separate the porous manganese dioxide catalyst (present in the liquid phase) and the catalyst particles (residue).

[0043] The residue was mixed with 20 kg of Na2O2 and NaOH (mass ratio 1:0.75), and placed in an electric furnace for alkali fusion at 650°C for 2.5 hours. The alkali fusion product was added to 100 L of deionized water, stirred at 95°C for 3 hours, filtered, and the filtrate was collected. The filtrate was acidified with 98% sulfuric acid to pH = 1, heated to 95°C, and 10 wt% NaClO3 was added dropwise until the solution turned yellow. Stirring was continued for 30 minutes, and the generated RuO4 gas was absorbed with 36% hydrochloric acid to obtain a ruthenium trichloride solution.

[0044] Example 5: This example provides a method for preparing ruthenium trichloride.

[0045] Petroleum chemical waste ruthenium alumina catalyst 20 kg (from a hydrogenation device of a certain petrochemical enterprise, appearance is gray-black cylindrical particles, ruthenium content is about 0.5 wt%, carbon content is about 8 wt%). The particle size was 2-10 mm, and the catalyst was dried to constant weight. Porous manganese dioxide catalyst 0.5 kg, average particle size 3 μm, specific surface area 90 m 2 / g, prepared by sol-gel method. The specific method is as follows: potassium permanganate is dissolved in deionized water, sodium citrate is added as a complexing agent, the pH is adjusted to 7-8, and the obtained sol is dried at 120°C for 12 hours. The dried material is calcined in air at 400°C for 4 hours, ground through a 100 mesh sieve, and the porous manganese dioxide powder with an average particle size of 3 μm and a specific surface area of 90 m 2 / g is obtained.

[0046] The mixture was transferred to a vertical pyrolysis furnace, and CO2 gas (purity 99.99%, flow rate 3000 L / h) was pre-injected into the furnace for 30 minutes to replace air. The stirring device was started, and the rotation speed was set to 400 rpm. The heating rate was 10°C / min, and the temperature was raised to 650°C and kept constant for 3 hours. During this period, CO2 gas was continuously injected, and the pressure in the furnace was kept positive (0.02 MPa).

[0047] After the calcination was completed, the heating was stopped, and the temperature was naturally cooled to room temperature. The stirring and CO2 injection were continued until the temperature dropped below 100°C. After cooling, the calcined product was transferred to a 500 L polypropylene stirring tank, 60 L of 30% hydrochloric acid was added for leaching, and the mixture was stirred at 95°C for 2 hours. Then, 300 L of deionized water was added, and the mixture was stirred at high speed for 20 min and treated with ultrasonic waves for 10 min (power 1 kW, frequency 40 kHz). The mixture was filtered (filter screen aperture 20 μm), and the porous manganese dioxide catalyst (present in the liquid phase) and the catalyst particles (residue) were separated.

[0048] The residue was mixed with 20 kg of Na2O2 and NaOH (mass ratio 1:1), and placed in an electric furnace for alkali fusion at 700 °C for 2 hours. The alkali fusion product was added to 100 L of deionized water, stirred at 95 °C for 3 hours, filtered, and the filtrate was collected. The filtrate was acidified with 98% sulfuric acid to pH = 1, heated to 95 °C, and 10 wt% NaClO3 was added dropwise until the solution turned yellow. The stirring was continued for 30 minutes, and the generated RuO4 gas was absorbed with 36% hydrochloric acid to obtain a ruthenium trichloride solution.

[0049] Example 6: This example provides a method for preparing ruthenium trichloride.

[0050] Petroleum chemical waste ruthenium alumina catalyst 20 kg (from a hydrogenation device of a certain petrochemical enterprise, appearance is gray-black cylindrical particles, ruthenium content is about 0.5 wt%, carbon content is about 8 wt%). The particle size was 2-10 mm, and the catalyst was dried to constant weight. Porous manganese dioxide catalyst 0.5 kg, average particle size 5 μm, specific surface area 80 m 2 / g, prepared by sol-gel method. The specific method is as follows: potassium permanganate is dissolved in deionized water, sodium citrate is added as a complexing agent, the pH is adjusted to 7-8, and the obtained sol is dried at 120 °C for 12 hours. The dried material is calcined in air at 400 °C for 4 hours, ground through a 100 mesh sieve, and the porous manganese dioxide powder with an average particle size of 5 μm and a specific surface area of 80 m 2 / g is obtained.

[0051] The mixture was transferred to a vertical pyrolysis furnace, and CO2 gas (purity 99.99%, flow rate 3000 L / h) was pre-injected into the furnace for 30 minutes to replace air. The stirring device was started, and the rotation speed was set to 400 rpm. The heating rate was 10 °C / min, and the temperature was raised to 650 °C and held for 3.5 hours. During this period, CO2 gas was continuously injected, and the pressure in the furnace was maintained at 0.02 MPa.

[0052] After the calcination was completed, the heating was stopped, and the temperature was naturally cooled to room temperature. The stirring and CO2 injection were continued until the temperature dropped below 100 °C. After cooling, the calcined product was transferred to a 500 L polypropylene stirring tank, 60 L of 30% hydrochloric acid was added for leaching, and the mixture was stirred at 95 °C for 2 hours. The mixture was then pressure-filtered, 300 L of deionized water was added, and the mixture was stirred at high speed for 20 min. The mixture was then treated with ultrasonic waves for 10 min (power 1 kW, frequency 40 kHz), filtered (filter screen aperture 20 μm), and the porous manganese dioxide catalyst (present in the liquid phase) and the catalyst particles (residue) were separated.

[0053] The residue was mixed with 20 kg of Na2O2 and NaOH (mass ratio 1:0.75), and placed in an electric furnace for alkali fusion at 650°C for 2.5 hours. The alkali fusion product was added to 100 L of deionized water, stirred at 95°C for 3 hours, filtered, and the filtrate was collected. The filtrate was acidified with 98% sulfuric acid to pH = 1, heated to 95°C, and 10 wt% NaClO3 was added dropwise until the solution turned yellow. The stirring was continued for 30 minutes, and the generated RuO4 gas was absorbed with 36% hydrochloric acid to obtain a ruthenium trichloride solution.

[0054] Example 7: This example provides a method for preparing ruthenium trichloride.

[0055] Petroleum chemical waste ruthenium alumina catalyst 20 kg (from a hydrogenation device of a certain petrochemical enterprise, appearance is gray-black cylindrical particles, ruthenium content is about 0.5 wt%, carbon content is about 8 wt%). The particle size was 2-10 mm, and the catalyst was dried to constant weight. Porous manganese dioxide catalyst 0.2 kg, average particle size 1 μm, specific surface area 140 m 2 / g, prepared by sol-gel method. The specific method is as follows: potassium permanganate is dissolved in deionized water, sodium citrate is added as a complexing agent, the pH is adjusted to 7-8, and the obtained sol is dried at 120°C for 12 hours. The dried material is calcined in air at 400°C for 4 hours, ground through a 100 mesh sieve, and the porous manganese dioxide powder with an average particle size of 1 μm and a specific surface area of 140 m 2 / g is obtained.

[0056] The mixture was transferred to a vertical pyrolysis furnace, and CO2 gas (purity 99.99%, flow rate 3000 L / h) was introduced into the furnace body for 30 minutes to replace the air. The stirring device was started, and the rotation speed was set to 300 rpm. The heating rate was 10°C / min, and the temperature was raised to 620°C and kept constant for 3 hours. During this period, CO2 gas was continuously introduced, and the pressure in the furnace was kept positive (0.02 MPa).

[0057] After the calcination was completed, the heating was stopped, and the temperature was naturally cooled to room temperature. The stirring and CO2 gas were continued until the temperature dropped below 100°C. After cooling, the calcined product was transferred to a 500 L polypropylene stirring tank, 60 L of 30% hydrochloric acid was added for leaching, and the mixture was stirred at 95°C for 2 hours. Then, 300 L of deionized water was added, and the mixture was stirred at high speed for 20 min, treated with ultrasonic waves for 10 min (power 1 kW, frequency 40 kHz), filtered (filter screen aperture 10 μm), and the porous manganese dioxide catalyst (present in the liquid phase) and the catalyst particles (residue) were separated.

[0058] The residue was mixed with 20 kg of Na2O2 and NaOH (mass ratio 1:0.75), and placed in an electric furnace for alkali fusion at 650°C for 2.5 hours. The alkali fusion product was added to 100 L of deionized water, stirred at 95°C for 3 hours, filtered, and the filtrate was collected. The filtrate was acidified with 98% sulfuric acid to pH = 1, heated to 95°C, and 10 wt% NaClO3 was added dropwise until the solution turned yellow. Stirring was continued for 30 minutes, and the generated RuO4 gas was absorbed with 36% hydrochloric acid to obtain a ruthenium trichloride solution.

[0059] Example 8: This example provides a method for preparing ruthenium trichloride.

[0060] Petroleum chemical waste ruthenium alumina catalyst 20 kg (from a hydrogenation device of a certain petrochemical enterprise, appearance is gray-black cylindrical particles, ruthenium content is about 0.5 wt%, carbon content is about 8 wt%). The particle size was 2-10 mm, and the catalyst was dried to constant weight. Porous manganese dioxide catalyst 0.67 kg, average particle size 3 μm, specific surface area 90 m 2 / g, prepared by sol-gel method. Specifically, potassium permanganate was dissolved in deionized water, sodium citrate was added as a complexing agent, the pH was adjusted to 7-8, and the mixture was stirred in a 60°C water bath for 2 hours. The obtained sol was dried at 120°C for 12 hours, and the dried material was calcined in air at 400°C for 4 hours. The calcined material was ground through a 100 mesh sieve to obtain porous manganese dioxide powder with an average particle size of 3 μm and a specific surface area of 90 m 2 / g.

[0061] The mixture was transferred to a vertical pyrolysis furnace, and CO2 gas (purity 99.99%, flow rate 3000 L / h) was introduced into the furnace for 30 minutes to replace the air. The stirring device was started, and the rotation speed was set to 400 rpm. The temperature was raised at a rate of 10°C / min, and after reaching 700°C, the temperature was kept constant for 1.5 hours. During this period, CO2 gas was continuously introduced, and the pressure in the furnace was maintained at 0.02 MPa.

[0062] After the calcination was completed, the heating was stopped, and the mixture was naturally cooled to room temperature. The stirring and CO2 gas introduction were continued until the temperature dropped below 100°C. After cooling, the calcined product was transferred to a 500 L polypropylene stirring tank, 60 L of 30% hydrochloric acid was added for leaching, and the mixture was stirred at 95°C for 2 hours. The mixture was then pressure-filtered, 300 L of deionized water was added, and the mixture was stirred at high speed for 20 min. Ultrasonic treatment was performed for 10 min (power 1 kW, frequency 40 kHz), and the mixture was filtered (filter screen aperture 50 μm) to separate the porous manganese dioxide catalyst (present in the liquid phase) and the catalyst particles (residue).

[0063] The filter residue was mixed with 20 kg of Na2O2 and NaOH (mass ratio 1:0.75), placed in an electric furnace, and alkali melted at 650°C for 2.5 hours. The alkali melting product was added to 100 L of deionized water, stirred at 95°C for 3 hours, filtered, and the filtrate was collected. The filtrate was acidified with 40% sulfuric acid to pH=1, heated to 90°C, and 10wt% NaClO3 was added dropwise until the solution turned yellow. The stirring was continued for 30 minutes, and the generated RuO4 gas was absorbed with 30% hydrochloric acid to obtain a ruthenium trichloride solution.

[0064] Comparative Example 1: This comparative example provides a method for preparing ruthenium trichloride.

[0065] Petroleum chemical waste ruthenium alumina catalyst 20 kg (from a hydrogenation device of a certain petrochemical enterprise, appearance is gray-black cylindrical particles, ruthenium content is about 0.5wt%, carbon content is about 8wt%). The particle size was 2-10 mm, and the catalyst was dried to constant weight.

[0066] The catalyst was transferred to a vertical pyrolysis furnace, and air was pre-injected into the furnace body (flow rate 3000 L / h) for 30 minutes. The stirring device was started, and the rotation speed was set to 400 rpm. The heating rate was 10°C / min, and the temperature was raised to 650°C and kept constant for 3 hours. During this period, air was continuously injected, and the pressure in the furnace was maintained at 0.02 MPa.

[0067] After the calcination was completed, the heating was stopped, and the temperature was naturally cooled to room temperature. The stirring and aeration were continued until the temperature dropped below 100°C. After cooling, the calcined product was transferred to a 500 L polypropylene stirring tank, 60 L of 30% hydrochloric acid was added for leaching, and the mixture was stirred at 95°C for 2 hours. The mixture was then pressure-filtered, 300 L of deionized water was added, and the mixture was stirred at high speed for 20 min. The mixture was then treated with ultrasonic waves for 10 min (power 1 kW, frequency 40 kHz), filtered (filter screen aperture 20 μm), and the catalyst particles (filter residue) were separated.

[0068] The filter residue was mixed with 20 kg of Na2O2 and NaOH (mass ratio 1:0.75), placed in an electric furnace, and alkali melted at 650°C for 2.5 hours. The alkali melting product was added to 100 L of deionized water, stirred at 95°C for 3 hours, filtered, and the filtrate was collected. The filtrate was acidified with 40% sulfuric acid to pH=1, heated to 90°C, and 10wt% NaClO3 was added dropwise until the solution turned yellow. The stirring was continued for 30 minutes, and the generated RuO4 gas was absorbed with 30% hydrochloric acid to obtain a ruthenium trichloride solution.

[0069] Comparative Example 2: This comparative example provides a method for preparing ruthenium trichloride.

[0070] Petroleum waste ruthenium-alumina catalyst 20 kg (from a hydrogenation unit of a certain petrochemical enterprise, appearance is gray-black cylindrical particles, containing about 0.5wt% ruthenium, containing about 8wt% carbon.), particle size 2-10 mm, dried to constant weight.

[0071] The catalyst was transferred to a vertical pyrolysis furnace, and CO2 gas (purity 99.99%, flow rate 3000 L / h) was introduced into the furnace body for 30 minutes to replace the air. Start the stirring device and set the rotation speed to 400 rpm. The temperature rising rate is 10℃ / min, and after rising to 650℃, it is kept constant for 3 hours, during which CO2 gas is continuously introduced, and the positive pressure (0.02 MPa) in the furnace is maintained.

[0072] After the calcination was completed, the heating was stopped, and the natural cooling to room temperature was carried out, and the stirring and CO2 aeration were continued until the temperature dropped below 100℃. After cooling, the calcined product was transferred to a 500 L polypropylene stirring tank, 60 L of 30% hydrochloric acid was added for leaching, stirred at 95℃ for 2 hours, pressure filtration, then 300 L of deionized water was added, high-speed stirring for 20 min, ultrasonic treatment for 10 min (power 1kW, frequency 40kHz), filtration (filter screen aperture 20μm), and the catalyst particles (filtration residue) were separated.

[0073] The filtration residue was mixed with 20 kg of Na2O2 and NaOH (mass ratio 1:0.75), placed in an electric furnace, and alkali melted at 650℃ for 2.5 hours. The alkali melting product was added to 100 L of deionized water, stirred at 95℃ for 3 hours, filtered, and the filtrate was collected. The filtrate was acidified with 98% sulfuric acid to pH=1, the temperature was raised to 95℃, 10wt% NaClO3 was added dropwise until the solution turned yellow, and the stirring was continued for 30 minutes. The generated RuO4 gas was absorbed with 36% hydrochloric acid to obtain a ruthenium trichloride solution.

[0074] Comparative Example 3: This comparative example provides a method for preparing ruthenium trichloride.

[0075] Petroleum waste ruthenium-alumina catalyst 20 kg (from a hydrogenation unit of a certain petrochemical enterprise, appearance is gray-black cylindrical particles, containing about 0.5wt% ruthenium, containing about 8wt% carbon.), particle size 2-10 mm, dried to constant weight. Porous manganese dioxide catalyst 0.5 kg, average particle size 50μm, commercially available.

[0076] The mixture was transferred to a vertical pyrolysis furnace, and CO2 gas (purity 99.99%, flow rate 3000 L / h) was introduced into the furnace body for 30 minutes to replace the air. Start the stirring device and set the rotation speed to 400 rpm. The temperature rising rate is 10℃ / min, and after rising to 650℃, it is kept constant for 3 hours, during which CO2 gas is continuously introduced, and the positive pressure (0.02 MPa) in the furnace is maintained.

[0077] After the roasting, the heating was stopped and the product was allowed to cool naturally to room temperature. The stirring and CO2 bubbling were continued until the temperature dropped to below 100°C. After cooling, the roasted product was transferred to a 500 L polypropylene stirred tank, 60 L of 30% hydrochloric acid was added, and the mixture was stirred at 95°C for 2 hours. The product was then filtered under pressure, and 300 L of deionized water was added. The mixture was stirred at high speed for 20 min and treated with ultrasound for 10 min (power 1 kW, frequency 40 kHz). The mixture was then filtered (filter mesh size 20 μm) to separate the porous manganese dioxide catalyst (present in the liquid phase) from the catalyst particles (filtrate).

[0078] The filtrate was mixed with 20 kg of Na2O2 and NaOH (mass ratio 1:0.75) and placed in an electric furnace. The mixture was subjected to alkaline fusion at 650°C for 2.5 hours. The product of the alkaline fusion was added to 100 L of deionized water and stirred at 95°C for 3 hours. The mixture was then filtered, and the filtrate was collected. The filtrate was acidified with 98% sulfuric acid until the pH reached 1. The mixture was heated to 95°C, and 10 wt% NaClO3 was added dropwise until the solution turned yellow. The mixture was stirred for 30 min, and the RuO4 gas generated was absorbed with 36% hydrochloric acid to obtain a solution of ruthenium trichloride.

[0079] The ruthenium recovery rate and the carbon removal rate of the above process were determined.

[0080] Ruthenium recovery rate: The ruthenium content of the product solution of ruthenium trichloride was determined by ICP-OES, and the original ruthenium content in the catalyst was compared to calculate the recovery rate.

[0081] Carbon removal rate: The catalyst particles before and after roasting were sampled, and the carbon content was determined by TGA thermogravimetric analysis to calculate the removal rate.

[0082] The test data of the examples and comparative examples are shown in the following table.

[0083] Table 1. Ruthenium recovery rate and carbon removal rate of the examples and comparative examples.

[0084] No. Firing time (h) Ruthenium recovery (%) Carbon deposition removal rate (%) Example 1 3 99.3 97.8 Example 2 2.5 99.5 98.6 Example 3 3 99.1 97.2 Example 4 2 99.6 99.0 Example 5 3 99.2 97.5 Example 6 3.5 98.7 95.8 Example 7 3 98.8 96.8 Example 8 1.5 99.1 97.6 Comparative Example 1 3 93.8 98.5 Comparative Example 2 3 85.2 38.2 Comparative Example 3 3 90.0 83.2

[0085] As can be seen from Table 1, all the examples achieve high ruthenium recovery (98.7% or more) and coke removal rate (95.8% or more), short calcination time, and high recovery of the auxiliary agent, which embodies the high efficiency and green recycling characteristics of the process. In comparison, Comparative Example 1 uses an air atmosphere, so its coke removal rate is high, but part of the ruthenium is oxidized to form ruthenium dioxide and then volatilized, resulting in a decrease in the recovery of ruthenium; Comparative Example 2 uses a carbon dioxide atmosphere but does not add manganese dioxide, so the reaction efficiency of coke and carbon dioxide is too low, and the coke removal rate is too low, which will result in difficulty in fully releasing ruthenium in the subsequent acid leaching and alkali melting processes; Comparative Example 3 uses conventional manganese dioxide, although its ruthenium recovery and coke removal rate are improved compared with those of Comparative Example 2, but because its particle size is too large, far larger than the size of the catalyst pores, it is difficult to enter the interior of the catalyst, and cannot effectively strip and catalyze to remove deep-layer coke, part of the ruthenium is still coated inside the coke, and it is difficult to fully dissolve out the ruthenium in the subsequent acid leaching and alkali melting steps, resulting in a ruthenium recovery rate lower than that of Example 1 and also lower than that of Comparative Example 1 calcined under an air atmosphere.

[0086] Any combination of the technical features of the above-described examples can be made, and to make the description concise, all possible combinations of the technical features in the above-described examples are not described, however, as long as the combination of the technical features does not exist, it should be considered as the scope of the description.

[0087] The above-described examples only express several embodiments of the present application, and the description is more specific and detailed, but it should not be understood as limiting the scope of the patent. It should be noted that for ordinary skilled persons in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which are within the scope of protection of the present application. Therefore, the scope of protection of the patent of the present application should be subject to the appended claims.

Claims

1. A process for the preparation of ruthenium trichloride, characterized in that, The method comprises the following steps: (1) mixing the waste ruthenium-alumina catalyst with a porous manganese dioxide catalyst, the specific surface area of the porous manganese dioxide catalyst is not less than 80 m2 / g, the average particle size is 1-5 μm, and the mass ratio of the catalyst to the waste ruthenium-alumina catalyst is (1-5):100; (2) placing the mixture in a vertical pyrolysis furnace with a mechanical stirring device, roasting the mixture under a CO2 atmosphere at 620-650 ℃ for 2-3.5 hours, and the stirring speed is 300-500 rpm; (3) cooling after the roasting is completed, carrying out hydrochloric acid leaching, solid-liquid separation, alkali fusion, water leaching, acidification and oxidative distillation to obtain a ruthenium trichloride solution, and the porous manganese dioxide catalyst is prepared by a sol-gel method.

2. The production method according to claim 1, characterized by, The specific surface area of the porous manganese dioxide catalyst is 90-120 m 2 / g.

3. The preparation method according to claim 1, characterized in that, The solid-liquid separation uses a filter screen with a pore size of 10-50 μm.

4. The preparation method according to claim 1, characterized in that, The alkali fusion step comprises mixing the catalyst after the hydrochloric acid leaching with Na2O2 and NaOH, and carrying out alkali fusion at 600-700 ℃ for 1.5-3 hours.

5. The production method according to claim 4, characterized by, The mass ratio of the Na2O2 to the NaOH is 1:0.75-1:

1.

6. The method of claim 1, wherein, The acidification step comprises adding sulfuric acid with a mass fraction of 40-98% dropwise to the water leaching filtrate of the alkali fusion product, and heating to 90-100 ℃.

7. The preparation method according to claim 1, characterized in that, The oxidative distillation step comprises adding NaClO3 dropwise to the acidification liquid to oxidize Ru to RuO4, and absorbing with hydrochloric acid with a mass fraction of 30-37% to obtain a ruthenium trichloride solution.

8. The method of claim 1, wherein, The stirring speed in the roasting step is 350-450 rpm.

9. The method of claim 1, wherein, The mass ratio of the porous manganese dioxide catalyst to the waste ruthenium-alumina catalyst is 1:30 to 1:40.

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