Coal gangue catalyst carrier preparation and performance optimization method
By removing impurity ions with dilute acid solution, preparing a porous framework by adding forming agents and template agents, performing one-step calcination and surface modification, ultrasonically dispersing the active components, and regenerating the catalyst using a green recycling process, the problem of low performance recovery of coal gangue catalyst carriers in existing technologies has been solved, achieving efficient and economical catalyst performance optimization.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-10-16
- Publication Date
- 2026-03-10
AI Technical Summary
In existing coal gangue catalyst support preparation processes, there are limited improvements in purity, improper selection of molding agents, inaccurate control of porous structure, poor calcination effect, poor compatibility of modifiers, unstable nano-dispersion, insufficient mechanical strength and thermal stability, and incomplete green recycling, making it difficult to achieve high-efficiency catalytic performance.
Impurity ions are removed by dilute acid solution, a porous framework is prepared by adding a forming agent and a template agent, followed by one-step calcination and surface modification, ultrasonic dispersion of active components, and regeneration of the catalyst using a green recycling process to optimize mechanical strength and thermal stability.
It significantly improves the purity and porous structure of coal gangue catalyst support, enhances the loading capacity and dispersion effect of active components, improves the mechanical strength and thermal stability of catalyst, realizes efficient recycling, and reduces the cost of use.
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Figure CN121623772A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of coal gangue treatment, in particular to a coal gangue catalyst carrier preparation and performance optimization method. BACKGROUND
[0002] Coal gangue, as a major solid waste associated with coal, occupies a large amount of land resources and may cause many environmental problems. In recent years, researchers have attempted to use coal gangue to prepare catalyst carriers to achieve resource recycling.
[0003] However, the existing coal gangue catalyst carrier preparation process still has many shortcomings. On the one hand, during acidification pretreatment, the key parameters such as the concentration of dilute acid solution, treatment temperature and time are not precisely optimized, resulting in limited improvement of coal gangue purity, which is difficult to meet the demand of high-performance catalyst carriers. On the other hand, the addition amount and type of forming agent in the forming process are chosen randomly, without fully considering the interaction between the forming agent and coal gangue, making it difficult to balance the shape stability and porous structure construction of the carrier. In the preparation process of porous framework, the conditions are not fine enough, and the pore structure of the carrier cannot be precisely controlled, which limits the loading amount and dispersion effect of active components. In addition, the key factors such as temperature setting, heating rate and holding time in the staged calcination process are not effectively integrated, resulting in incomplete removal of organic matter and moisture, poor sintering effect, and further affecting the crystallinity and mechanical strength of the coal gangue carrier. In the chemical modification technology, the modified agent has poor compatibility with the surface of the coal gangue carrier, making it difficult to form a stable and efficient modified layer, which limits the loading efficiency of active components and the improvement of catalytic performance. The application of nano dispersion technology also has the problem of unstable dispersion effect, which makes it difficult to ensure the uniform and high dispersion of active components on the surface of the carrier. In the post-processing step, the conditions such as drying and calcination are not fully optimized, resulting in insignificant improvement of the mechanical strength and thermal stability of the coal gangue catalyst carrier. Finally, the green recycling process faces challenges such as incomplete removal of toxic substances and low performance recovery degree in actual operation, and has not achieved efficient and economic carrier recycling. SUMMARY
[0004] The purpose of the present application is to provide a coal gangue catalyst carrier preparation and performance optimization method, which aims to solve the problem of low performance recovery degree of coal gangue catalyst carrier in the prior art.
[0005] To achieve the above-mentioned purpose, the present application provides a coal gangue catalyst carrier preparation and performance optimization method, which comprises the following steps: Through acidification pretreatment, impurity ions are removed from coal gangue with a dilute acid solution to obtain purified coal gangue; After adding a forming agent to the treated coal gangue and mixing uniformly, a coal gangue blank is formed; The coal gangue blank is prepared into a porous framework by using a template agent method to obtain a porous coal gangue carrier; The porous framework is subjected to one-step calcination to obtain a calcined coal gangue carrier; The surface of the calcined coal gangue carrier is modified to obtain a modified coal gangue carrier; An active component precursor is added to the modified coal gangue carrier to obtain a coal gangue catalyst loaded with the active component; The mechanical strength and thermal stability of the coal gangue catalyst loaded with the active component are improved to obtain a performance-optimized coal gangue catalyst; The used coal gangue catalyst is subjected to regeneration treatment by using a green recycling process.
[0006] In the "coal gangue is pretreated by acidification to remove impurity ions with a dilute acid solution to obtain purified coal gangue", the following steps are included: The coal gangue is soaked in a dilute sulfuric acid solution to fully dissolve the impurity ions in the acid solution; The soaked coal gangue is filtered to remove the acid solution and dissolved impurity ions; The coal gangue is repeatedly washed with deionized water until the washed water is neutral to obtain purified coal gangue.
[0007] In the "molding agent is added to the treated coal gangue and uniformly mixed to form a coal gangue blank", the following steps are included: 10% of the molding agent is weighed according to the mass of the coal gangue; The molding agent is uniformly mixed with the purified coal gangue to uniformly coat the molding agent on the surface of the coal gangue particles; The mixed material is placed in a molding device and pressed under a certain pressure to obtain a coal gangue blank.
[0008] In the "coal gangue blank is prepared into a porous framework by using a template agent method to obtain a porous coal gangue carrier", the following steps are included: 5% of the template agent is weighed according to the mass of the coal gangue and uniformly mixed with the coal gangue blank; The mixed coal gangue blank is aged to form pore structures in the coal gangue blank with the template agent; The aged coal gangue blank is dried to obtain a porous coal gangue carrier.
[0009] In the "the porous framework is subjected to one-step calcination to obtain a calcined coal gangue carrier", the following steps are included: The porous coal gangue carrier is placed in a muffle furnace to fully remove the organic matter and moisture in the coal gangue carrier; After calcination, the furnace is cooled to room temperature to obtain a calcined coal gangue carrier.
[0010] wherein, in the "modification of the surface of the calcined coal gangue carrier to obtain a modified coal gangue carrier", the following steps are included: A silane coupling agent KH550 solution with a mass fraction of 2% is prepared; The calcined coal gangue carrier is immersed in the solution for 4 hours, so that the silane coupling agent is fully adsorbed on the surface of the coal gangue carrier; The immersed coal gangue carrier is taken out, dried, and then placed in an oven to obtain the modified coal gangue carrier.
[0011] wherein, in the "addition of active component precursor to the modified coal gangue carrier to obtain a coal gangue catalyst loaded with active component", the following steps are included: The active component precursor is weighed and dissolved in an appropriate amount of deionized water to prepare an active component precursor solution; The modified coal gangue carrier is immersed in the active component precursor solution, so that the active component is uniformly dispersed on the surface of the coal gangue carrier; The immersed coal gangue carrier is taken out, dried, and then placed in an oven to obtain the coal gangue catalyst loaded with active component.
[0012] The coal gangue catalyst carrier preparation and performance optimization method of the present application significantly improves the performance of the coal gangue catalyst carrier through a series of optimization steps. Acidification pretreatment effectively removes impurities, improves the purity of coal gangue, and provides high-quality raw materials for subsequent operations. The forming process ensures the stability of the coal gangue blank and the construction of the porous structure. The template method precisely prepares the porous skeleton, optimizes the specific surface area and pore characteristics of the carrier, and increases the loading sites of the active component. The one-step calcination process removes organic matter and moisture, enhances the sintering effect, and improves the crystallinity and mechanical strength of the carrier. Surface modification significantly enhances the loading capacity of the carrier and promotes the uniform dispersion of the active component. The ultrasonic dispersion technology realizes the highly uniform dispersion of the active component, improving the activity of the catalyst. The post-treatment further optimizes the mechanical strength and thermal stability of the carrier, prolonging the service life of the catalyst. The green recycling process effectively reduces the use cost, reduces waste emissions, and realizes efficient recycling of the catalyst, providing an environmentally friendly and economic solution for the high-value utilization of coal gangue. Thus, the problem of low performance recovery degree of the coal gangue catalyst carrier in the prior art is solved. BRIEF DESCRIPTION OF DRAWINGS
[0013] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0014] Figure 1 This is a flowchart of the method for preparing and optimizing the performance of coal gangue catalyst support provided by the present invention.
[0015] Figure 2 The flowchart describes a process of removing impurity ions from coal gangue using a dilute acid solution through an acidification pretreatment operation to obtain purified coal gangue.
[0016] Figure 3 The flowchart describes the process of adding a molding agent to treated coal gangue, mixing it evenly, and then molding it to obtain a coal gangue blank.
[0017] Figure 4 This is a flowchart of a process for preparing a porous skeleton from coal gangue blanks using a template agent method to obtain a porous coal gangue carrier.
[0018] Figure 5 This is a flowchart of a process for calcining a porous framework to obtain a calcined coal gangue carrier.
[0019] Figure 6 This is a flowchart of modifying the surface of calcined coal gangue carrier to obtain modified coal gangue carrier.
[0020] Figure 7 This is a flowchart of adding an active component precursor to a modified coal gangue support to obtain a coal gangue catalyst loaded with the active component.
[0021] Figure 8 This is a flowchart illustrating how to improve the mechanical strength and thermal stability of a coal gangue catalyst supported on an active component, thereby obtaining a coal gangue catalyst with optimized performance.
[0022] Figure 9 This is a flowchart illustrating the regeneration process of used coal gangue catalysts using a green recycling technology. Detailed Implementation
[0023] 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.
[0024] Please see Figures 1 to 9This invention provides a method for preparing and optimizing the performance of a coal gangue catalyst support, comprising the following steps: S1 uses an acidification pretreatment process to remove impurity ions from coal gangue with a dilute acid solution to obtain purified coal gangue. S11 involves immersing the coal gangue in a dilute sulfuric acid solution to fully dissolve the impurity ions in the acid. Specifically, firstly, the coal gangue is crushed to a particle size of less than 1 mm to increase the contact area with the acid solution and improve the dissolution efficiency of impurity ions. Then, the coal gangue is mixed with a 15% (w / w) dilute sulfuric acid solution at a solid-liquid ratio of 1:5 (g / mL), and placed in a constant-temperature water bath at 60°C for 2 hours with stirring. During the soaking process, continuous stirring ensures full contact between the coal gangue and the acid solution, guaranteeing that impurity ions (such as calcium, magnesium, and iron) are fully dissolved in the acid.
[0025] S12 filters the soaked coal gangue to remove acid and dissolved impurity ions; Specifically, after soaking, the mixture is poured into a filter and vacuum filtered to separate the acid and dissolved impurities from the coal gangue solids. After filtration, the coal gangue is preliminarily rinsed with deionized water to remove residual acid.
[0026] S13 uses deionized water to repeatedly rinse the coal gangue until the rinse water is neutral, thus obtaining purified coal gangue.
[0027] Specifically, the filtered coal gangue is placed in a washing tank and repeatedly rinsed with deionized water. After each rinse, the rinse water is collected and its acidity or alkalinity is tested using pH test paper. When the pH value of the rinse water is close to 7, the rinsing is considered qualified, at which point the coal gangue has been purified and the content of impurity ions has been significantly reduced.
[0028] S2 adds a molding agent to the treated coal gangue, mixes it evenly, and then shapes it to obtain a coal gangue blank. S21. Take 10% of the coal gangue mass as the molding agent; Specifically, accurately weigh the coal gangue after acidification pretreatment, and weigh out 10% of its mass as a molding agent. The molding agent is a mixture of clay and bentonite in a 1:1 mass ratio to ensure that the coal gangue billet has good molding properties and an appropriate pore structure.
[0029] S22 mixes the molding agent with highly purified coal gangue evenly, so that the molding agent is evenly coated on the surface of the coal gangue particles. Specifically, the forming agent is added to the purified coal gangue and placed in a high-speed mixer, where it is stirred for 15 minutes at a speed of 500 rpm. Stirring ensures that the forming agent is evenly coated on the surface of the coal gangue particles, forming a homogeneous mixture.
[0030] S23 places the mixed materials into a molding device and presses them under a certain pressure to obtain a coal gangue billet.
[0031] Specifically, the uniformly mixed materials are placed in a molding die and pressed into shape using a tablet press at a pressure of 10 MPa to obtain a coal gangue billet with a certain shape and strength. The formed billet is then naturally dried at room temperature for 24 hours to enhance its strength and stability.
[0032] S3 uses a template agent method to prepare a porous skeleton from coal gangue blanks to obtain a porous coal gangue carrier; S31 Weigh out 5% of the template agent according to the mass of coal gangue, and mix it evenly with the coal gangue blank; Specifically, accurately weigh the mass of the coal gangue billet, and weigh out 5% of the template agent P123 by mass. Add the template agent to the coal gangue billet, place it in a mixer, and stir at 300 r / min for 10 minutes to ensure that the template agent is evenly dispersed in the coal gangue billet.
[0033] S32 ages the mixed coal gangue billet, allowing the template agent to form a porous structure in the coal gangue billet; Specifically, the mixed coal gangue blanks are placed in a sealed container and aged at 60°C for 24 hours. During the aging process, the template agent P123 gradually undergoes self-assembly in the coal gangue blanks, forming an ordered pore structure.
[0034] S33 dries the aged coal gangue blank to obtain a porous coal gangue carrier.
[0035] Specifically, the aged coal gangue blanks are removed from the sealed container and placed in a ventilated and dry place to dry naturally at room temperature for 12 hours. Then, the dried blanks are placed in a forced-air drying oven and dried at 80°C for 6 hours to obtain a coal gangue carrier with a rich porous structure.
[0036] S4 is used to calcine the porous skeleton in one step to obtain the calcined coal gangue carrier. S41 places the porous coal gangue carrier in a muffle furnace to fully remove organic matter and moisture from the coal gangue carrier; Specifically, the porous coal gangue carrier is placed in a muffle furnace and heated to 300°C at a heating rate of 5°C / min, and held at that temperature for 2 hours. During this process, the moisture and organic matter such as the template agent in the coal gangue carrier gradually volatilize and decompose, and are fully removed.
[0037] After S42 is calcined, it is cooled to room temperature in the furnace to obtain the calcined coal gangue carrier.
[0038] Specifically, after holding at 300℃, the temperature is increased to 850℃ at a rate of 5℃ / min and held for 3 hours. After calcination, the power to the muffle furnace is turned off, allowing the coal gangue carrier to cool to room temperature within the furnace. This step aims to remove residual organic matter and moisture through high-temperature calcination, while simultaneously making the crystal structure of the coal gangue carrier more compact and stable.
[0039] S5 modifies the surface of calcined coal gangue carrier to obtain modified coal gangue carrier. S51 prepares a 2% (w / w) solution of silane coupling agent KH550; Specifically, accurately weigh an appropriate amount of silane coupling agent KH550, dissolve it in deionized water, and prepare a 2% (w / w) solution. To ensure the solution is homogeneous, stir it on a magnetic stirrer for 30 minutes.
[0040] S52 immerses the calcined coal gangue carrier in the solution for 4 hours to allow the silane coupling agent to be fully adsorbed on the surface of the coal gangue carrier. Specifically, the calcined coal gangue carrier is placed in a prepared solution of silane coupling agent KH550, ensuring that the carrier is completely submerged in the solution. It is then allowed to stand at room temperature for 4 hours to allow the silane coupling agent molecules to fully adsorb onto the surface and pores of the coal gangue carrier.
[0041] S53 After the impregnated coal gangue carrier is taken out and dried, it is placed in an oven to obtain the modified coal gangue carrier.
[0042] Specifically, after impregnation, the coal gangue carrier is removed from the solution and placed in a ventilated area to dry. Then, the dried carrier is placed in an oven and dried at 100°C for 2 hours to allow the silane coupling agent to form stable chemical bonds on the carrier surface, thus obtaining the modified coal gangue carrier.
[0043] S6 adds an active component precursor to the modified coal gangue support to obtain a coal gangue catalyst loaded with active components. S61 Weigh out the active component precursor and dissolve it in an appropriate amount of deionized water to prepare an active component precursor solution; Specifically, based on the required active components of the target catalyst, accurately weigh an appropriate amount of precursor (such as copper nitrate, ferric nitrate, etc.). Dissolve the weighed precursor in deionized water to prepare a solution of appropriate concentration. For example, to prepare a 0.1 mol / L copper nitrate solution, accurately weigh 2.396 g of copper nitrate. (Cu(NO3)2・3H2O) dissolved in 100mL of deionized water.
[0044] S62 impregnates the modified coal gangue carrier in an active component precursor solution, so that the active component is uniformly dispersed on the surface of the coal gangue carrier. Specifically, the modified coal gangue carrier is placed in the active component precursor solution, ensuring that the carrier is completely immersed in the solution. Ultrasonic dispersion technology is used, with the ultrasonic power set to 200W and the dispersion time set to 40 minutes, to uniformly disperse the active component precursor on the surface and in the pores of the coal gangue carrier.
[0045] S63 involves removing the impregnated coal gangue carrier, drying it, and then placing it in an oven to obtain a coal gangue catalyst loaded with active components.
[0046] Specifically, after impregnation, the coal gangue support is removed from the solution and placed in a ventilated area to dry. Then, the dried support is placed in an oven and dried at 80°C for 12 hours, so that the active component precursor forms a uniform precipitate or adsorption layer on the surface of the support, thus obtaining a coal gangue catalyst loaded with the active component.
[0047] S7 improves the mechanical strength and thermal stability of the coal gangue catalyst supported on the active component, resulting in a coal gangue catalyst with optimized performance. S71 involves calcining the coal gangue catalyst loaded with active components in a muffle furnace to ensure thorough integration of the active components with the coal gangue support; Specifically, the coal gangue catalyst loaded with active components is placed in a muffle furnace and heated to 550°C at a heating rate of 5°C / min, and held at that temperature for 3 hours. During the calcination process, the active components undergo chemical reactions and interdiffusion with the coal gangue support, forming more stable active sites, while simultaneously enhancing the mechanical strength and thermal stability of the support.
[0048] After S72 is calcined, it is cooled to room temperature in the furnace to obtain a coal gangue catalyst with optimized performance.
[0049] Specifically, after roasting, the power to the muffle furnace is turned off, allowing the coal gangue catalyst to cool to room temperature inside the furnace. This step aims to ensure that the roasted catalyst maintains its structural integrity during cooling, avoiding internal stress concentration and structural damage caused by rapid cooling, thereby obtaining a coal gangue catalyst with optimized performance.
[0050] S8 employs a green recycling process to regenerate used coal gangue catalysts.
[0051] S81 recycles the used coal gangue catalyst, removing surface dust and impurities; Specifically, after the coal gangue catalyst is used, it is removed from the reaction device. First, the surface dust and large particles of impurities are gently brushed away with a brush or soft brush. Then, the catalyst is quickly rinsed with deionized water to remove soluble salts and small particles of impurities from the surface.
[0052] S82 uses ethanol to ultrasonically clean the coal gangue catalyst to remove surface carbon deposits and metallic impurities; Specifically, the pre-cleaned coal gangue catalyst was placed in an ethanol solution with a volume ratio of ethanol to catalyst of 5:1 (mL / g). Ultrasonic cleaning was employed, with an ultrasonic power of 150W and a cleaning time of 30 minutes. The cavitation effect of ultrasound effectively removed carbon deposits and metallic impurities from the catalyst surface, resulting in a clean catalyst surface.
[0053] S83 places the cleaned coal gangue catalyst in a muffle furnace to activate it, thereby realizing the recycling of the coal gangue catalyst.
[0054] Specifically, the ultrasonically cleaned coal gangue catalyst is placed in a muffle furnace and heated to 300°C at a rate of 5°C / min under air atmosphere, and held at that temperature for 2 hours. This appropriate high-temperature treatment restores and regenerates the active sites on the catalyst surface, while further removing residual impurities. The activated coal gangue catalyst exhibits a certain degree of performance recovery and can be reused in catalytic reactions, achieving recycling.
[0055] The above-disclosed embodiments are merely preferred embodiments of the method for preparing and optimizing the performance of coal gangue catalyst support according to the present invention. Of course, they should not be construed as limiting the scope of the present invention. Those skilled in the art can understand that implementing all or part of the above-described embodiments and making equivalent changes in accordance with the claims of the present invention are still within the scope of the invention.
Claims
1. A method for preparation and performance optimization of coal gangue catalyst carrier, characterized in that, The method comprises the following steps: The coal gangue is pretreated by acidification to remove impurity ions with a dilute acid solution to obtain purified coal gangue; The treated coal gangue is mixed with a forming agent and then formed to obtain a coal gangue body; The coal gangue body is prepared into a porous framework by a template agent method to obtain a porous coal gangue carrier; The porous framework is calcined in one step to obtain a calcined coal gangue carrier; The surface of the calcined coal gangue carrier is modified to obtain a modified coal gangue carrier; An active component precursor is added to the modified coal gangue carrier to obtain a coal gangue catalyst loaded with the active component; The mechanical strength and thermal stability of the coal gangue catalyst loaded with the active component are improved to obtain a performance-optimized coal gangue catalyst; The used coal gangue catalyst is regenerated by a green recycling process.
2. The method of coal gangue catalyst support preparation and performance optimization of claim 1, wherein, In the step of "pretreating the coal gangue by acidification to remove impurity ions with a dilute acid solution to obtain purified coal gangue", the following steps are included: The coal gangue is soaked in a dilute sulfuric acid solution to fully dissolve the impurity ions in the acid solution; The soaked coal gangue is filtered to remove the acid solution and the dissolved impurity ions; The coal gangue is repeatedly washed with deionized water until the washed water is neutral to obtain the purified coal gangue.
3. The method of coal gangue catalyst support preparation and performance optimization of claim 1, wherein, In the step of "mixing the treated coal gangue with a forming agent and then forming to obtain a coal gangue body", the following steps are included: 10% of the forming agent is weighed according to the mass of the coal gangue; The forming agent is uniformly mixed with the purified coal gangue to uniformly coat the forming agent on the surface of the coal gangue particles; The mixed material is placed in a forming device and pressed under a certain pressure to form the coal gangue body.
4. The method of coal gangue catalyst support preparation and performance optimization of claim 1, wherein, In the step of "preparing a porous framework from the coal gangue body by a template agent method to obtain a porous coal gangue carrier", the following steps are included: 5% of the template agent is weighed according to the mass of the coal gangue and uniformly mixed with the coal gangue body; The mixed coal gangue body is aged to form pore structures in the coal gangue body with the template agent; The aged coal gangue body is dried to obtain the porous coal gangue carrier.
5. The method of coal refuse catalyst support preparation and performance optimization of claim 1, wherein, In the step of "calcining the porous framework in one step to obtain a calcined coal gangue carrier", the following steps are included: The porous coal gangue carrier is placed in a muffle furnace to fully remove the organic matter and moisture in the coal gangue carrier; After calcination is completed, the furnace is cooled to room temperature to obtain the calcined coal gangue carrier.
6. The method of preparing and optimizing the performance of a coal refuse catalyst support of claim 1, wherein, In the step of "modifying the surface of the calcined coal gangue carrier to obtain a modified coal gangue carrier", the following steps are included: A silane coupling agent KH550 solution with a mass fraction of 2% is prepared; The calcined coal gangue carrier is immersed in the solution for 4 hours to allow the silane coupling agent to be fully adsorbed on the surface of the coal gangue carrier; The immersed coal gangue carrier is taken out, dried, and then placed in an oven to obtain the modified coal gangue carrier.
7. The method of coal refuse catalyst support preparation and performance optimization of claim 1, wherein, In the step of "adding an active component precursor to the modified coal gangue carrier to obtain a coal gangue catalyst loaded with the active component", the following steps are included: The active component precursor is weighed, dissolved in a proper amount of deionized water, and prepared into an active component precursor solution; The modified coal gangue carrier is dipped in a solution of a precursor of the active component, so that the active component is uniformly dispersed on the surface of the coal gangue carrier; The dipped coal gangue carrier is taken out, dried, and then placed in an oven to obtain a coal gangue catalyst loaded with the active component.