Ruthenium-based catalyst for purifying fan blade pyrolysis waste gas as well as preparation method and application of ruthenium-based catalyst
By preparing ruthenium-based catalysts, the problems of high ignition temperature and easy poisoning in the purification of exhaust gas from the pyrolysis of wind turbine blades were solved, achieving low-cost and high-efficiency exhaust gas purification, especially the degradation of VOCs and CO.
Patent Information
- Application Number
- CN202511379710.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-25
- Publication Date
- 2026-01-13
AI Technical Summary
Existing catalysts have problems such as high ignition temperature, low catalytic activity, easy poisoning and high cost when treating pyrolysis exhaust gas from wind turbine blades. They are difficult to effectively purify complex exhaust gas components such as VOCs, CO, CH4 and halogen-containing compounds.
A ruthenium-based catalyst was prepared by reacting bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II) with 1,1,1-tris(diphenylphosphinemethyl)ethane under an inert gas atmosphere to generate a ruthenium(II)phosphine complex. The ruthenium-based catalyst was then prepared by cooling, crystallization, and vacuum drying, and applied to the purification of exhaust gas from the pyrolysis of wind turbine blades.
It significantly reduces the ignition temperature and complete oxidation temperature of exhaust gas, has good resistance to halogen poisoning, a long service life and relatively controllable cost, and can efficiently degrade pollutants such as VOCs and CO.
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Figure CN121319062A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of waste gas purification catalyst materials, and in particular to a ruthenium-based catalyst for purifying waste gas from the pyrolysis of wind turbine blades, its preparation method, and its application. Background Technology
[0002] With the rapid development of the wind power industry, the environmental treatment of a large number of retired wind turbine blades has become a serious challenge. Pyrolysis technology is one of the mainstream methods for treating blades, but the exhaust gas it produces is complex, often containing VOCs, CO, H2, CH4, as well as halogenated compounds such as bromine (Br) produced by the decomposition of epoxy resin, making it difficult to treat.
[0003] Currently, the catalysts used for treating organic waste gas mainly include ordinary metal oxide catalysts (such as CuFe2O4, MnO). x Metal oxide catalysts (such as Pt and Pd) have problems such as high ignition temperature and low catalytic activity. For recalcitrant components (such as CH4) and halogen-containing waste gases, the purification effect is not good and they are easily poisoned and deactivated. Although noble metal catalysts have high activity, they are expensive and equally sensitive to halogens, which limits their application in large-scale industrial waste gas treatment.
[0004] Therefore, there is an urgent need to develop a new type of catalyst that is highly active, resistant to poisoning, has a long lifespan, and is relatively cost-controllable, in order to solve the technical bottleneck of purifying exhaust gas from the pyrolysis of wind turbine blades. Summary of the Invention
[0005] The present invention aims to at least partially solve one of the technical problems in the related art.
[0006] Therefore, embodiments of the present invention propose a ruthenium-based catalyst for purifying exhaust gas from the pyrolysis of wind turbine blades, its preparation method, and its application.
[0007] In a first aspect, the present invention proposes a method for preparing a ruthenium-based catalyst for purifying exhaust gas from the pyrolysis of wind turbine blades, comprising the following steps:
[0008] (1) Under inert gas, a solid raw material consisting of bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II) and 1,1,1-tris(diphenylphosphinemethyl)ethane was added to a pressure-resistant tube, a solvent was added, and the tube was sealed and placed in a high-temperature magnetic stirrer to react and obtain a crude catalyst product.
[0009] (2) After the reaction is complete, cool to room temperature, add mixed solution to dissolve the crude catalyst product, and then refrigerate the pressure tube to allow crystals to precipitate.
[0010] (3) Crystals were obtained by filtration and separation, and then washed and vacuum dried to obtain ruthenium-based catalyst.
[0011] Furthermore, the mass ratio of bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II) to 1,1,1-tris(diphenylphosphinemethyl)ethane is 1:(2-3).
[0012] Furthermore, the bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II) is obtained by recycling and extracting ruthenium-containing waste.
[0013] Furthermore, in step (1), the reaction temperature in the high-temperature magnetic stirrer is 130-150°C, the reaction time is 2-4 hours, and the stirring speed is 600-700 rpm.
[0014] Furthermore, the inert gas includes one of nitrogen, helium, and argon.
[0015] Furthermore, the solvent includes one of toluene, dichloromethane, and tetrahydrofuran.
[0016] Furthermore, the mixed solution is a mixture of dichloromethane and pentane.
[0017] Furthermore, in step (2), the refrigeration temperature is -80 to -60°C, and the time is 48 to 72 hours.
[0018] Furthermore, in step (3), the vacuum drying temperature is 60-70°C and the time is 10-12 hours.
[0019] Furthermore, in step (3), the washing is performed 2 to 4 times with cold pentane.
[0020] Secondly, the present invention provides a ruthenium-based catalyst prepared by the method described in the first aspect above.
[0021] Thirdly, the present invention proposes the application of ruthenium-based catalysts prepared by the method proposed in the first aspect or the ruthenium-based catalysts proposed in the second aspect in the purification of exhaust gas from the pyrolysis of wind turbine blades.
[0022] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0023] The catalyst of this invention can significantly reduce the ignition temperature and complete oxidation temperature of pyrolysis waste gas, maintain stable activity in HBr gas, exhibit resistance to halogen poisoning, have a long lifespan, and low production cost. Attached Figure Description
[0024] The above and / or additional aspects and advantages of the present invention will become apparent and readily understood from the following description of the embodiments taken in conjunction with the accompanying drawings, wherein:
[0025] Figure 1This is a flowchart illustrating the preparation method of the ruthenium-based catalyst for purifying exhaust gas from the pyrolysis of wind turbine blades according to the present invention. Detailed Implementation
[0026] Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the accompanying drawings are exemplary and intended to explain the present invention, and should not be construed as limiting the present invention.
[0027] The following description, in conjunction with the accompanying drawings, describes the ruthenium-based catalyst for purifying exhaust gas from the pyrolysis of wind turbine blades, its preparation method, and its application.
[0028] like Figure 1 As shown, the preparation method of the ruthenium-based catalyst for purifying exhaust gas from wind turbine blade pyrolysis according to the present invention includes the following steps:
[0029] (1) Under inert gas, a solid raw material consisting of bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II) and 1,1,1-tris(diphenylphosphinemethyl)ethane was added to a pressure-resistant tube, a solvent was added, and the tube was sealed and placed in a high-temperature magnetic stirrer to react and obtain a crude catalyst product.
[0030] (2) After the reaction is complete, cool to room temperature, add mixed solution to dissolve the crude catalyst product, and then refrigerate the pressure tube to allow crystals to precipitate.
[0031] (3) Crystals were obtained by filtration and separation, and then washed and vacuum dried to obtain ruthenium-based catalyst.
[0032] Step (1) is the process of obtaining the crude catalyst product by reacting. A solid raw material composed of bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II) and 1,1,1-tris(diphenylphosphinemethyl)ethane is weighed, and the solid raw material is added to a pressure-resistant tube under inert gas conditions. A solvent is added, and then the pressure-resistant tube is placed in a high-temperature magnetic stirrer to react and obtain the crude catalyst product.
[0033] The core of the reaction between bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II) and 1,1,1-tris(diphenylphosphinemethyl)ethane is the substitution of the unstable 1,5-cyclooctadiene ligand by the phosphine ligand to generate a well-defined ruthenium(II)phosphine complex with catalytic activity.
[0034] In some embodiments, the mass ratio of bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II) to 1,1,1-tris(diphenylphosphinemethyl)ethane is 1:(2-3). It is understood that the mass ratio of bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II) to 1,1,1-tris(diphenylphosphinemethyl)ethane can be 1:2, 1:2.5, 1:3, or any value within the range of any two of these values.
[0035] In some embodiments, bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II) is obtained by recycling ruthenium-containing waste, thereby reducing costs, wherein the ruthenium-containing waste includes waste electronic products or waste catalysts.
[0036] In some embodiments, the reaction temperature in the high-temperature magnetic stirrer is 130–150°C, the reaction time is 2–4 hours, and the stirring speed is 600–700 rpm. It is understood that the reaction temperature can be 130°C, 140°C, 150°C, or any combination of two values; the reaction time can be 2 hours, 3 hours, 4 hours, or any combination of two values; and the stirring speed can be 600 rpm, 650 rpm, 700 rpm, or any combination of two values.
[0037] In some embodiments, the inert gas includes one of nitrogen, helium, and argon, and the flow rate of the inert gas is 2.0 to 3.0 N / min.
[0038] In some embodiments, the solvent includes one of toluene, dichloromethane, and tetrahydrofuran, and the amount of solvent added per 100 mg of bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II) is 0.8 to 1.0 mL.
[0039] Step (2) is the crystal precipitation process. After the reaction is completed, the mixture is cooled to room temperature, a mixed solution is added to dissolve the crude catalyst product, and then the pressure-resistant tube is refrigerated to allow the crystals to precipitate.
[0040] In some embodiments, the mixed solution is a mixture of dichloromethane and pentane, wherein the amount of dichloromethane added per 100 mg of bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II) is 1.6 to 2.4 mL, and the amount of pentane added per 100 mg of bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II) is 3.6 to 4.4 mL.
[0041] In some embodiments, the refrigeration temperature is -80 to -60°C, and the time is 48 to 72 hours. It is understood that the refrigeration temperature can be -80°C, -70°C, -60°C, or any combination of two values; the refrigeration time can be 48 hours, 60 hours, 72 hours, or any combination of two values.
[0042] Step (3) is the vacuum drying process of the crystal. After the crystal precipitates, it is separated by filtration to obtain the crystal, and then washed and vacuum dried to obtain the ruthenium-based catalyst.
[0043] In some embodiments, washing is performed 2 to 4 times with cold pentane.
[0044] In some embodiments, the vacuum drying temperature is 60–70°C, and the time is 10–12 hours. It is understood that the vacuum drying temperature can be 60°C, 65°C, 70°C, or any combination of two values; the vacuum drying time can be 10 hours, 11 hours, 12 hours, or any combination of two values.
[0045] The ruthenium-based catalyst is prepared by the method of the present invention. The ruthenium-based catalyst of the present invention is applied to the field of pyrolysis exhaust gas purification of wind turbine blades, that is, the catalyst of the present invention is used in catalytic combustion technology to efficiently degrade pollutants such as volatile organic compounds (VOCs) and carbon monoxide (CO) in exhaust gas and resist halogen poisoning.
[0046] The present invention will now be described in detail with reference to specific embodiments.
[0047] Example 1
[0048] In a nitrogen glove box with a flow rate of 3.0 N / min, weigh 1.0 g of bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II) and 2.0 g of 1,1,1-tris(diphenylphosphinemethyl)ethane, add them to a 100 mL pressure-resistant tube, then add 8 mL of toluene solvent, seal the pressure-resistant tube and place it in a high-temperature magnetic stirrer at 145 °C, and stir the reaction at 650 rpm for 3 hours.
[0049] After the reaction was completed, the mixture was cooled to room temperature, and 16 mL of dichloromethane and 36 mL of pentane were added and stirred until homogeneous. Then, the pressure-resistant tube was placed in a -70°C environment for 48 hours to allow crystals to precipitate.
[0050] The precipitated crystals were filtered, washed three times with cold pentane, and then dried at 65°C under vacuum for 11 hours to obtain a ruthenium-based catalyst.
[0051] Example 2
[0052] In a nitrogen glove box with a flow rate of 3.0 N / min, weigh 1.0 g of bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II) and 2.5 g of 1,1,1-tris(diphenylphosphinemethyl)ethane, add them to a 100 mL pressure-resistant tube, then add 8 mL of toluene solvent, seal the pressure-resistant tube and place it in a high-temperature magnetic stirrer at 145 °C, and stir the reaction at 650 rpm for 3 hours.
[0053] After the reaction was completed, the mixture was cooled to room temperature, and 16 mL of dichloromethane and 36 mL of pentane were added and stirred until homogeneous. Then, the pressure-resistant tube was placed in a -70°C environment for 48 hours to allow crystals to precipitate.
[0054] The precipitated crystals were filtered, washed three times with cold pentane, and then dried at 65°C under vacuum for 11 hours to obtain a ruthenium-based catalyst.
[0055] Example 3
[0056] In a nitrogen glove box with a flow rate of 3.0 N / min, weigh 1.0 g of bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II) and 3.0 g of 1,1,1-tris(diphenylphosphinemethyl)ethane, add them to a 100 mL pressure-resistant tube, then add 8 mL of toluene solvent, seal the pressure-resistant tube and place it in a high-temperature magnetic stirrer at 145 °C, and stir the reaction at 650 rpm for 3 hours.
[0057] After the reaction was completed, the mixture was cooled to room temperature, and 16 mL of dichloromethane and 36 mL of pentane were added and stirred until homogeneous. Then, the pressure-resistant tube was placed in a -70°C environment for 48 hours to allow crystals to precipitate.
[0058] The precipitated crystals were filtered, washed three times with cold pentane, and then dried at 65°C under vacuum for 11 hours to obtain a ruthenium-based catalyst.
[0059] Example 4
[0060] In a nitrogen glove box with a flow rate of 3.0 N / min, weigh 1.0 g of bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II) and 2.0 g of 1,1,1-tris(diphenylphosphinemethyl)ethane, add them to a 100 mL pressure-resistant tube, then add 8 mL of toluene solvent, seal the pressure-resistant tube and place it in a high-temperature magnetic stirrer at 130 °C, and stir the reaction at 650 rpm for 4 hours.
[0061] After the reaction was completed, the mixture was cooled to room temperature, and 16 mL of dichloromethane and 36 mL of pentane were added and stirred until homogeneous. Then, the pressure-resistant tube was placed in a -70°C environment for 48 hours to allow crystals to precipitate.
[0062] The precipitated crystals were filtered, washed three times with cold pentane, and then dried at 65°C under vacuum for 11 hours to obtain a ruthenium-based catalyst.
[0063] Example 5
[0064] In a nitrogen glove box with a flow rate of 3.0 N / min, weigh 1.0 g of bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II) and 2.0 g of 1,1,1-tris(diphenylphosphinemethyl)ethane, add them to a 100 mL pressure-resistant tube, then add 8 mL of toluene solvent, seal the pressure-resistant tube and place it in a high-temperature magnetic stirrer at 150 °C, and stir the reaction at 650 rpm for 2 hours.
[0065] After the reaction was completed, the mixture was cooled to room temperature, and 16 mL of dichloromethane and 36 mL of pentane were added and stirred until homogeneous. Then, the pressure-resistant tube was placed in a -70°C environment for 48 hours to allow crystals to precipitate.
[0066] The precipitated crystals were filtered, washed three times with cold pentane, and then dried at 65°C under vacuum for 11 hours to obtain a ruthenium-based catalyst.
[0067] Example 6
[0068] In a nitrogen glove box with a flow rate of 3.0 N / min, weigh 1.0 g of bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II) and 2.0 g of 1,1,1-tris(diphenylphosphinemethyl)ethane, add them to a 100 mL pressure-resistant tube, then add 8 mL of toluene solvent, seal the pressure-resistant tube and place it in a high-temperature magnetic stirrer at 145 °C, and stir the reaction at 650 rpm for 3 hours.
[0069] After the reaction was completed, the mixture was cooled to room temperature, and 16 mL of dichloromethane and 36 mL of pentane were added and stirred until homogeneous. Then, the pressure-resistant tube was placed in a -60°C environment for 72 hours to allow crystals to precipitate.
[0070] The precipitated crystals were filtered, washed three times with cold pentane, and then dried at 65°C under vacuum for 11 hours to obtain a ruthenium-based catalyst.
[0071] Test case
[0072] At an air speed of 10,000 m 3 h -1Under the specified conditions, catalytic combustion tests were conducted using the catalyst prepared in Example 1, a commercially available vanadium-titanium catalyst, and a commercially available alumina catalyst. The test results are shown in Table 1 below. T50 is the reaction temperature required for the catalyst to achieve a conversion rate of 50%, and T90 is the reaction temperature required for the catalyst to achieve a conversion rate of 90%. The exhaust gas contained CO, CH4, C3H6, toluene, and 100 ppm HBr. The commercially available vanadium-titanium catalyst had a pore size of 30*30 and a pore diameter of 4.2 mm, while the commercially available alumina catalyst had a pore volume ≥0.45 ml / g.
[0073] Table 1:
[0074] Example 1 Commercially available vanadium-titanium catalysts Commercially available alumina catalysts CO ignition temperature 160 230 240 T50 temperature of CO 185 265 285 T90 temperature of CO 210 300 325 ignition temperature of toluene 190 265 345 T50 temperature of toluene 230 290 385 T90 temperature of toluene 270 325 420 HBr removal rate >95％ ＜50％ ＜70％
[0075] As can be seen from Table 1, the T90 temperatures of toluene and CO of the catalyst in Example 1 are lower than those of the commercial vanadium-titanium catalyst and the alumina catalyst, and the removal rate of HBr is higher. It is evident that the catalyst in Example 1 can significantly reduce the ignition temperature and complete oxidation temperature of the pyrolysis waste gas. In the simulated waste gas containing HBr, the activity remains stable, while the activity of the commercial vanadium-titanium catalyst and the alumina catalyst decreases significantly.
[0076] In addition, the catalyst of Example 1 showed no significant activity decay during a continuous 100-hour test, demonstrating excellent performance and stability.
[0077] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms may refer to different embodiments or examples. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.
[0078] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of that feature. In the description of this invention, "a plurality of" means at least two, such as two, three, etc., unless otherwise explicitly specified.
[0079] Although embodiments of the invention have been shown and described, those skilled in the art will understand that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
Claims
1. A method for preparing a ruthenium-based catalyst for purifying exhaust gas from the pyrolysis of wind turbine blades, characterized in that, Includes the following steps: (1) Under inert gas, a solid raw material consisting of bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II) and 1,1,1-tris(diphenylphosphinemethyl)ethane was added to a pressure-resistant tube, a solvent was added, and the tube was sealed and placed in a high-temperature magnetic stirrer to react and obtain a crude catalyst product. (2) After the reaction is complete, cool to room temperature, add mixed solution to dissolve the crude catalyst product, and then refrigerate the pressure tube to allow crystals to precipitate. (3) Crystals were obtained by filtration and separation, and then washed and vacuum dried to obtain ruthenium-based catalyst.
2. The method as described in claim 1, characterized in that, The mass ratio of bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II) to 1,1,1-tris(diphenylphosphinemethyl)ethane is 1:(2-3).
3. The method as described in claim 1, characterized in that, The bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II) was obtained by recycling and extracting ruthenium-containing waste.
4. The method as described in claim 1, characterized in that, In step (1), the reaction temperature in the high-temperature magnetic stirrer is 130-150°C, the reaction time is 2-4 hours, and the stirring speed is 600-700 rpm.
5. The method as described in claim 1, characterized in that, The inert gas includes one of nitrogen, helium, and argon; And / or, the solvent includes one of toluene, dichloromethane, and tetrahydrofuran; And / or, the mixed solution is a mixture of dichloromethane and pentane.
6. The method as described in claim 1, characterized in that, In step (2), the refrigeration temperature is -80 to -60°C, and the time is 48 to 72 hours.
7. The method as described in claim 1, characterized in that, In step (3), the vacuum drying temperature is 60-70℃ and the time is 10-12h.
8. The method as described in claim 1, characterized in that, In step (3), the washing process involves washing with cold pentane 2 to 4 times.
9. The ruthenium-based catalyst prepared by the method according to any one of claims 1 to 8.
10. The application of the ruthenium-based catalyst prepared by the method according to any one of claims 1 to 8 or the ruthenium-based catalyst according to claim 9 in the purification of exhaust gas from the pyrolysis of wind turbine blades.