Method for detecting ruthenium content in ruthenium catalyst

Abstract

The invention discloses a method for detecting the content of ruthenium in a ruthenium catalyst, and belongs to the field of chemical material detection.The method includes the steps that after the ruthenium catalyst is ground, sodium hydroxide and potassium nitrate are added, salt in a crucible is dissolved with hot water after high-temperature melting is conducted, a sodium ruthenate solution is obtained, then sulfuric acid and a potassium permanganate solution are added, and stirring is conducted; the method comprises the following steps: adding sodium ruthenate into a hydrochloric acid solution, heating to oxidize the sodium ruthenate into ruthenium oxide, absorbing gaseous ruthenium oxide by the hydrochloric acid solution, fixing the volume, measuring by an inductively coupled plasma atomic emission spectrometer (ICP-OES) to obtain the concentration of ruthenium in the solution, and calculating to obtain the ruthenium content. According to the method, ruthenium in the ruthenium catalyst is converted into sodium ruthenate which is easy to dissolve through molten sodium hydroxide and potassium nitrate, the sodium ruthenate is changed into the ruthenium solution with a single component through oxidative distillation and hydrochloric acid absorption, the ruthenium content in the ruthenium catalyst is measured through the ICP method, the method is low in cost and high in accuracy, and a simple and accurate product control method can be provided for the production field; a good detection means is provided for the field of analysis and detection.

Description

Technical Field

[0001] The present invention relates to the field of chemical material detection, and in particular to a method for detecting the ruthenium content in a ruthenium catalyst. Background Art

[0002] Ruthenium catalysts are a class of catalytic materials with metallic ruthenium (Ru) as their core active component. Due to their unique electronic structure (e.g., variable oxidation states, strong coordination ability) and high catalytic performance, they are widely used in energy, chemical, and environmental protection sectors. Ruthenium content in ruthenium catalyst products is a key quality indicator. Ruthenium content in ruthenium catalysts can be determined by various methods, including the melting method, the chlorination method, and the pretreatment activation-dissolution method. The melting method offers superior decomposition efficiency and is therefore suitable for various catalyst types.

[0003] Sodium peroxide, commonly used in the fusion method, is an explosive and hazardous chemical with strong corrosive properties, and its use is regulated. Furthermore, if improperly stored, sodium peroxide rapidly absorbs carbon dioxide and moisture upon contact with air, deteriorating, reducing the effective sodium peroxide content in the reagent. This deteriorated sodium peroxide leads to an incomplete reaction, reducing the leaching rate of ruthenium, and causing the analyzed ruthenium content to be lower than the actual value. The nonferrous industry standard YS1207-2017, "Chemical Analysis Method for Ruthenium in Alumina-Based Ruthenium Materials - Determination of Ruthenium Content - Hydrogen Reduction Gravimetric Method," uses sodium peroxide fusion, oxidative distillation absorption, precipitation, and hydrogen reduction to determine the ruthenium content in ruthenium catalysts. This method involves multiple steps, and hydrogen reduction requires high equipment requirements and is somewhat hazardous. Since the ruthenium content in catalysts is generally low, the gravimetric method can produce highly volatile results. Chinese invention patent CN 101109700A discloses a method for determining the ruthenium content in a ruthenium-containing catalyst. This method involves melting and decomposing the ruthenium catalyst with potassium hydroxide. After cooling, excess hydrochloric acid is added to acidify the solution. Sample solutions and standard solutions are then prepared separately. Finally, the ruthenium content of the multi-component material is determined using an air-acetylene flame atomic absorption spectrometer. This method does not separate the matrix, and the working solution contains a high salt content, which may interfere with the measurement data.

[0004] Therefore, existing methods for determining the ruthenium content in ruthenium catalysts have low accuracy and cannot meet the quality requirements of ruthenium catalyst products. Therefore, there is an urgent need for an accurate method for determining the ruthenium content in ruthenium catalysts that meets the detection requirements of ruthenium catalysts. Summary of the Invention

[0005] Based on this, in order to solve the problem that the method for determining the ruthenium content in the ruthenium catalyst in the prior art has low accuracy and cannot meet the quality requirements of the ruthenium catalyst product, the present invention provides a method for detecting the ruthenium content in the ruthenium catalyst. The specific technical solution is as follows:

[0006] A method for detecting the ruthenium content in a ruthenium catalyst, the method comprising the following steps:

[0007] Step (1): grinding the ruthenium catalyst to obtain a ruthenium catalyst powder, then weighing the ruthenium catalyst powder sample to an accuracy of 0.0001 g, and placing the ruthenium catalyst sample in a crucible;

[0008] Step (2): adding reagents into the crucible and mixing the sample and reagents evenly;

[0009] Step (3): Cover the crucible and place it in a muffle furnace, heat it uniformly from room temperature and then cool it naturally;

[0010] Step (4): After cooling, remove the crucible, place it in a beaker, add water to cover the crucible, and heat and boil until the salt is completely dissolved;

[0011] Step (5): adding an acid solution to the above solution, heating, and absorbing the ruthenium oxide gas with a hydrochloric acid absorption solution;

[0012] Step (6): The hydrochloric acid absorption solution is diluted to a volumetric flask, and the ruthenium concentration is measured by inductively coupled plasma atomic emission spectrometry to calculate the ruthenium content in the ruthenium catalyst.

[0013] Furthermore, in step (1), the particle size of the ruthenium catalyst powder obtained after the grinding treatment is larger than a 200-mesh sieve.

[0014] Furthermore, in step (2), the reagents placed in the crucible are sodium hydroxide and potassium nitrate.

[0015] Furthermore, in step (2), the mass ratio of the ruthenium catalyst powder sample to the reagent is 1:20-50.

[0016] Furthermore, in step (3), the crucible is placed in a muffle furnace and heated to 400° C. to 800° C., and kept warm for 10 to 60 minutes.

[0017] Furthermore, in step (5), the acid solution added is sulfuric acid and potassium permanganate solution.

[0018] Furthermore, in step (5), the heating temperature is 80-100°C.

[0019] Furthermore, in step (5), the volume concentration of the hydrochloric acid absorption solution is 20%.

[0020] Furthermore, in step (6), the absorption solution is diluted to a volumetric flask, and the ruthenium concentration is measured at a wavelength of 240.272 nm using an inductively coupled plasma atomic emission spectrometer.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] The present invention utilizes molten sodium hydroxide and potassium nitrate to convert ruthenium in a ruthenium catalyst into easily soluble sodium ruthenate, which is then converted into a single-component ruthenium solution through oxidative distillation and hydrochloric acid absorption. The ruthenium content in the ruthenium catalyst is determined by an ICP method. The method has low cost, simple operation, high accuracy, and low loss to detection equipment. It can provide a simple and accurate product control method for the production field, and a good detection means for the analytical detection field, and is easy to promote and apply. DETAILED DESCRIPTION

[0023] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with its embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and do not limit the scope of protection of the present invention.

[0024] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this invention pertains. The terms used herein in the specification of the present invention are for the purpose of describing specific embodiments only and are not intended to limit the present invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0025] In one embodiment of the present invention, a method for detecting the ruthenium content in a ruthenium catalyst comprises the following steps:

[0026] Step (1): grinding the ruthenium catalyst to obtain a ruthenium catalyst powder, then weighing the ruthenium catalyst powder sample to an accuracy of 0.0001 g, and placing the ruthenium catalyst sample in a crucible;

[0027] Step (2): adding reagents into the crucible and mixing the sample and reagents evenly;

[0028] Step (3): Cover the crucible and place it in a muffle furnace, heat it uniformly from room temperature and then cool it naturally;

[0029] Step (4): After cooling, remove the crucible, place it in a beaker, add water to cover the crucible, and heat and boil until the salt is completely dissolved;

[0030] Step (5): adding an acid solution to the above solution, heating, and absorbing the ruthenium oxide gas with a hydrochloric acid absorption solution;

[0031] Step (6): The hydrochloric acid absorption solution is diluted to a volumetric flask, and the ruthenium concentration is measured by inductively coupled plasma atomic emission spectrometry to calculate the ruthenium content in the ruthenium catalyst.

[0032] In one embodiment, in step (1), the particle size of the ruthenium catalyst powder obtained after the grinding treatment is larger than a 200-mesh sieve.

[0033] In one embodiment, in step (2), the reagents placed in the crucible are sodium hydroxide and potassium nitrate.

[0034] In one embodiment, in step (2), the mass ratio of the ruthenium catalyst powder sample to the reagent is 1:20-50.

[0035] In one embodiment, in step (3), the crucible is placed in a muffle furnace and heated to 400° C. to 800° C., and kept warm for 10 to 60 minutes.

[0036] In one embodiment, in step (5), the acid solution added is sulfuric acid and potassium permanganate solution.

[0037] In one embodiment, in step (5), the heating temperature is 80-100°C.

[0038] In one embodiment, in step (5), the volume concentration of the hydrochloric acid absorption solution is 20%.

[0039] In one embodiment, in step (6), the absorption solution is diluted to a volumetric flask, and the ruthenium concentration is measured at a wavelength of 240.272 nm using an inductively coupled plasma atomic emission spectrometer.

[0040] The above scheme provides a method for detecting the ruthenium content in a ruthenium catalyst, which has high detection accuracy, is simple and efficient, has low raw material cost, and is easy to promote and apply.

[0041] The embodiments of the present invention will be described in detail below with reference to specific examples.

[0042] Example 1:

[0043] A method for detecting the ruthenium content in a ruthenium catalyst comprises the following steps:

[0044] Grinding the ruthenium catalyst to obtain a ruthenium catalyst powder having a particle size exceeding 200 mesh;

[0045] Weigh 0.20g of ruthenium catalyst powder and place it in a crucible. Add 2.0g of sodium hydroxide and 2.0g of potassium nitrate and mix thoroughly. Then, cover the crucible and place it in a muffle furnace. Raise the temperature to 400°C at a constant rate and hold for 20 minutes. After cooling, remove the crucible and place it in a 200mL beaker. Add water to cover the crucible and heat to a boil until the salts are completely dissolved.

[0046] The above solution was transferred to a ground-mouth conical flask, and 20 mL of sulfuric acid (1+1) and 10 mL of a saturated potassium permanganate solution were added. A glass ox-horn tube was added to the ground-mouth flask, and the outlet of the ox-horn tube was immersed in a 20% hydrochloric acid absorption solution. The temperature was controlled and heated until uniform bubbles emerged from the ox-horn tube outlet. The heating was maintained for 18 minutes. After the ruthenium oxide gas was completely absorbed by the hydrochloric acid absorption solution, the volume was fixed to a volumetric flask after cooling.

[0047] The ruthenium concentration was determined using an inductively coupled plasma atomic emission spectrometer, wherein the wavelength of the ruthenium element was selected to be 240.272 nm, and the ruthenium concentration was determined using a standard curve method.

[0048] The results of Example 1 are shown in Table 1.

[0049] Table 1: Ruthenium content in ruthenium catalyst

[0050]

[0051]

[0052] Example 2:

[0053] A method for detecting the ruthenium content in a ruthenium catalyst comprises the following steps:

[0054] Grinding the ruthenium catalyst to obtain a ruthenium catalyst powder having a particle size exceeding 200 mesh;

[0055] Weigh 0.10 g of ruthenium catalyst powder and place it in a crucible. Add 2.0 g of sodium hydroxide and 2.0 g of potassium nitrate and mix well. Then, cover the crucible and place it in a muffle furnace. Raise the temperature to 700°C at a constant rate and keep it warm for 15 minutes. After cooling, remove the crucible and place it in a 200 mL beaker. Add water to cover the crucible and heat to a boil until the salts are completely dissolved.

[0056] Transfer the above solution to a ground-mouth conical flask, add 20mL of sulfuric acid (1+1) and 10mL of saturated potassium permanganate solution, add a glass ox-horn tube to the ground-mouth flask, immerse the outlet of the ox-horn tube in an absorption solution containing 20% hydrochloric acid, control the temperature and heat until uniform bubbles emerge from the outlet of the ox-horn tube, keep heating for 20 minutes, wait until the ruthenium oxide gas is completely absorbed by the absorption liquid, cool and then adjust the volume to a volumetric flask.

[0057] The ruthenium concentration was determined using an inductively coupled plasma atomic emission spectrometer, wherein the wavelength of the ruthenium element was selected to be 240.272 nm, and the ruthenium concentration was determined using a standard curve method.

[0058] The results of Example 2 are shown in Table 2.

[0059] Table 2: Ruthenium content in ruthenium catalyst

[0060]

[0061]

[0062] Example 3:

[0063] A method for detecting the ruthenium content in a ruthenium catalyst comprises the following steps:

[0064] Grinding the ruthenium catalyst to obtain a ruthenium catalyst powder having a particle size exceeding 200 mesh;

[0065] Weigh 0.50 g of ruthenium catalyst powder and place it in a crucible. Add 4.0 g of sodium hydroxide and 2.0 g of potassium nitrate and mix well. Then, cover the crucible and place it in a muffle furnace. Raise the temperature to 700°C at a constant rate and keep it warm for 30 minutes. After cooling, remove the crucible and place it in a 200 mL beaker. Add water to cover the crucible and heat to a boil until the salts are completely dissolved.

[0066] The above solution was transferred to a ground-mouth conical flask, and 20 mL of sulfuric acid (1+1) and 10 mL of a saturated potassium permanganate solution were added. A glass ox-horn tube was added to the ground-mouth flask, and the outlet of the ox-horn tube was immersed in an absorption liquid containing a 20% hydrochloric acid absorption solution. The temperature was controlled and heated until uniform bubbles emerged from the ox-horn tube outlet. The heating was maintained for 20 min. After the ruthenium oxide gas was completely absorbed by the absorption liquid, the volume was fixed to a volumetric flask after cooling.

[0067] The ruthenium concentration was determined using an inductively coupled plasma atomic emission spectrometer, wherein the wavelength of the ruthenium element was selected to be 240.272 nm, and the ruthenium concentration was determined using a standard curve method.

[0068] The results of Example 3 are shown in Table 3.

[0069] Table 3: Ruthenium content in ruthenium catalyst

[0070] serial number Ruthenium content / % 1 0.572 2 0.550 3 0.556 4 0.549 5 0.581 6 0.563 7 0.557 average value 0.561 RSD 2.10

[0071] In summary, the present invention can provide a method for detecting the ruthenium content in a ruthenium catalyst, and the inspection results are highly accurate, easy to operate, and the overall process steps are simple and the method cost is low. It can provide a simple and accurate product control method for the production field, and provide a good detection means for the analytical detection field, which is easy to promote and apply.

[0072] The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0073] The above-described embodiments merely illustrate several implementations of the present invention, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be determined by the appended claims.

Claims

1. A method for detecting the ruthenium content in a ruthenium catalyst, characterized in that: The detection method comprises the following steps: Step (1): grinding the ruthenium catalyst to obtain a ruthenium catalyst powder, then weighing the ruthenium catalyst powder sample to an accuracy of 0.0001 g, and placing the ruthenium catalyst sample in a crucible; Step (2): adding reagents into the crucible and mixing the sample and reagents evenly; Step (3): Cover the crucible and place it in a muffle furnace, heat it uniformly from room temperature and then cool it naturally; Step (4): After cooling, remove the crucible, place it in a beaker, add water to cover the crucible, and heat and boil until the salt is completely dissolved; Step (5): adding an acid solution to the above solution, heating, and absorbing the ruthenium oxide gas with a hydrochloric acid absorption solution; Step (6): The hydrochloric acid absorption solution is diluted to a volumetric flask, and the ruthenium concentration is measured by inductively coupled plasma atomic emission spectrometry to calculate the ruthenium content in the ruthenium catalyst.

2. The detection method according to claim 1, wherein In step (1), the particle size of the ruthenium catalyst powder obtained after the grinding treatment is larger than a 200-mesh sieve.

3. The detection method according to claim 1, wherein In step (2), the reagents placed in the crucible are sodium hydroxide and potassium nitrate.

4. The detection method according to claim 1, wherein In step (2), the mass ratio of the ruthenium catalyst powder sample to the reagent is 1:20-50.

5. The detection method according to claim 1, wherein In step (3), the crucible is placed in a muffle furnace and heated to 400° C. to 800° C., and kept warm for 10 to 60 minutes.

6. The detection method according to claim 1, characterized in that In step (5), the acid solution added is sulfuric acid and potassium permanganate solution.

7. The detection method according to claim 1, characterized in that In step (5), the heating temperature is 80-100°C.

8. The detection method according to claim 1, wherein In step (5), the volume concentration of the hydrochloric acid absorption solution is 20%.

9. The detection method according to claim 1, wherein In step (6), the absorption solution is diluted to a volumetric flask, and the ruthenium concentration is measured at a wavelength of 240.272 nm using an inductively coupled plasma atomic emission spectrometer.

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