Denitration catalyst-based crushed material porous cleaning method
By improving the porous cleaning method and combining ultrasonic water washing, mixed cleaning solution and acid washing solution for dual cleaning, the problem of unsatisfactory cleaning effect of denitrification catalyst crushed material was solved, and efficient and low-cost catalyst recovery and regeneration were achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- GANSU QINGQIJI SIBILIN ENVIRONMENTAL PROTECTION TECH CO LTD
- Filing Date
- 2025-12-31
- Publication Date
- 2026-05-12
AI Technical Summary
In the existing technology, the cleaning method for crushed denitrification catalyst is not ideal, which makes it impossible to effectively recover valuable elements and poses an environmental pollution risk.
A cleaning method combining ultrasonic water washing, pure water rinsing, mixed cleaning solution (a mixture of triethanolamine, monoethanolamine, Triton X-100 and water) and acid washing solution (sulfuric acid and oxalic acid solution) is adopted. Through static and bubbling rotation cleaning, arsenic and deep alkali metals on the catalyst surface are removed, active sites are activated, and the microscopic specific surface area is increased.
It shortens cleaning time, improves cleaning efficiency, reduces production costs, increases product yield, reduces environmental pollution, and achieves efficient recovery and regeneration of catalysts.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of denitrification catalyst regeneration technology, and in particular to a method for porous cleaning of denitrification catalyst crushed material. Background Technology
[0002] With the increasing sophistication of SCR denitrification catalyst regeneration, some non-regenerable catalysts need to be processed. To avoid secondary pollution, catalyst crushing and grinding are used for recycling and refining. Valuable elements in the catalyst are recovered and refined to produce new catalysts, thus forming a closed loop.
[0003] Because refining places high demands on the catalyst, non-renewable catalysts must first be crushed and cleaned before effective refining. However, current methods for cleaning crushed materials are generally not very effective and therefore need to be improved. Summary of the Invention
[0004] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:
[0005] A method for porous cleaning of crushed material based on denitrification catalyst is provided, comprising the following steps:
[0006] Step 1. Place the crushed denitrification catalyst into pure water for ultrasonic washing;
[0007] Step 2. Place the washed denitrification catalyst crushed material into pure water for at least two bubbling rinses;
[0008] Step 3. Prepare a mixed cleaning solution by mixing sodium hydroxide solution and cleaning agent at a volume ratio of 7:3. The cleaning agent consists of the following components and their mass fractions: 10-15 parts triethanolamine, 5-10 parts monoethanolamine, 3-7 parts Triton X-100, and 80-90 parts water. Place the rinsed denitrification catalyst crushed material into the mixed cleaning solution, heat to 65°C, let it stand for 35 minutes for cleaning, and then bubble and rotate for 35 minutes for cleaning.
[0009] Step 4. Place the cleaned denitrification catalyst crushed material into pure water for bubble washing;
[0010] Step 5. Prepare an acid washing solution by mixing sulfuric acid and oxalic acid. Put the crushed denitrification catalyst into the acid washing solution and let it stand for 35 minutes at room temperature. Then, bubble and rotate the solution for 30 minutes.
[0011] Step 6. Rinse the crushed denitrification catalyst material in pure water and then remove it.
[0012] In a preferred embodiment of the present invention, in step 2, the first bubbling rinse lasts for 25 minutes, and the second bubbling rinse lasts for 15 minutes.
[0013] In a preferred embodiment of the present invention, in step 3, the solubility of sodium hydroxide solution is 0.5%-1%.
[0014] In a preferred embodiment of the present invention, the concentration of sulfuric acid in the pickling solution is 0.05 mol / L, and the concentration of oxalic acid in the pickling solution is 0.02 mol / L.
[0015] The beneficial effects of this invention are: by improving and optimizing the process steps, the cleaning time is reasonably shortened, the cleaning efficiency is improved, and the production cost is reduced. At the same time, the dual cleaning method of mixed cleaning solution and pickling solution is adopted, which effectively improves the cleaning effect and thus improves the product yield. Detailed Implementation
[0016] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0017] The embodiments of the present invention include:
[0018] A method for porous cleaning of crushed material based on denitrification catalyst, comprising the following steps:
[0019] Step 1. Place the crushed denitrification catalyst into pure water and ultrasonically wash for 20 minutes.
[0020] Step 2. Place the washed denitrification catalyst crushed material into pure water for a bubble rinsing for 25 minutes.
[0021] Step 3. Place the crushed denitrification catalyst into pure water for a second bubbling rinse for 15 minutes.
[0022] Step 4. Prepare a mixed cleaning solution by mixing sodium hydroxide solution and cleaning agent at a volume ratio of 7:3. The components and mass fractions of the cleaning agent include: 10-15 parts triethanolamine, 5-10 parts monoethanolamine, 3-7 parts Triton X-100, and 80-90 parts water. Place the rinsed denitrification catalyst crushed material into the mixed cleaning solution, heat to 65°C, let it stand for 35 minutes for cleaning, and then bubble and rotate for 35 minutes for cleaning.
[0023] Furthermore, the solubility of sodium hydroxide solution is 0.5%-1%.
[0024] Furthermore, triethanolamine can be replaced with monoethanolamine without changing the mass fraction.
[0025] Sodium hydroxide can effectively remove arsenic from the surface of catalyst flakes (arsenic is an important element that causes catalyst poisoning and reduces the catalyst's lifespan). At the same time, it can also clean the catalyst micropores, increase the microscopic specific surface area, and activate active sites, laying a solid foundation for subsequent regeneration and remanufacturing.
[0026] Compared to other cleaning agents, the mixed cleaning solution obtained by mixing sodium hydroxide with the cleaning agent used in this application is currently the agent that almost does not cause other problems. As shown in the table below (shaded areas are for key reference): Through cleaning, the mixed cleaning solution can effectively remove elements such as potassium, sodium, and arsenic that are detrimental to the catalyst, while simultaneously increasing the TiO2 content of the catalyst, minimizing the leaching rates of WO3 and V2O5, and retaining their beneficial components. The remaining components are all within reasonable ranges and meet national standards.
[0027]
[0028] The following are the results of microstructure testing. After cleaning, the microscopic specific surface area increased significantly, and the internal channels were opened, laying a solid foundation for subsequent fabrication.
[0029]
[0030] As shown in the table below, the mixed cleaning solution cleans the catalyst by reacting with the components on the catalyst surface. This application employs a static + dynamic cleaning mode. The static mode involves immersing the catalyst in the cleaning solution, allowing the reagents to react with the catalyst itself. The dynamic mode replaces traditional bubbling with rotary bubbling. Rotation is added to ensure better cleaning of the flakes. If only bubbling is used, some flakes may react unevenly or insufficiently, making them difficult to clean thoroughly. Rotary bubbling solves the problem of cleaning without dead angles, ensuring cleaning efficiency while improving cleaning quality.
[0031]
[0032] Step 5. Place the cleaned denitrification catalyst crushed material into pure water and bubble wash for 45 minutes.
[0033] Step 6. Prepare an acid washing solution using sulfuric acid and oxalic acid. Place the crushed denitrification catalyst into the acid washing solution and allow it to stand for 35 minutes at room temperature, followed by bubbling and rotating washing for 30 minutes. The acid washing solution can effectively remove alkali metals (potassium and sodium) and alkaline earth metals from the surface and deeper layers of the catalyst.
[0034] Furthermore, the concentration of sulfuric acid in the pickling solution is 0.05 mol / L, and the concentration of oxalic acid in the pickling solution is 13 g / L.
[0035] Step 7. Rinse the crushed denitrification catalyst in pure water for 45 minutes and then remove it.
[0036] The beneficial effects of the present invention, a method for porous cleaning of crushed material based on denitrification catalyst, are as follows:
[0037] 1. Timeliness: By improving and optimizing the process steps, the cleaning time has been reasonably shortened, cleaning efficiency has been increased, production costs have been reduced, and the price of the product will also be reduced, thus better achieving a virtuous cycle in the market.
[0038] 2. Cleaning effect: The dual cleaning method of sodium hydroxide + cleaning agent and sulfuric acid + oxalic acid effectively improves the cleaning effect, thereby increasing the product yield.
[0039] 3. Process restructuring: A new flake cleaning process is used to efficiently clean the crushed catalyst (referred to as crushed material), which reduces cleaning and labor costs while meeting cleaning standards, thereby reducing secondary pollution to the environment and complying with national regulations.
[0040] The above description is merely an embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural or procedural transformations made based on the content of the present invention specification, or direct or indirect applications in other related technical fields, are similarly included within the patent protection scope of the present invention.
Claims
1. A method for porous cleaning of crushed material based on denitrification catalyst, characterized in that the steps include: include: Step 1. Place the crushed denitrification catalyst into pure water for ultrasonic washing; Step 2. Place the washed denitrification catalyst crushed material into pure water for at least two bubbling rinses; Step 3. Prepare a mixed cleaning solution by mixing sodium hydroxide solution and cleaning agent at a volume ratio of 7:
3. The cleaning agent consists of the following components and their mass fractions: 10-15 parts triethanolamine, 5-10 parts monoethanolamine, 3-7 parts Triton X-100, and 80-90 parts water. Place the rinsed denitrification catalyst crushed material into the mixed cleaning solution, heat to 65°C, let it stand for 35 minutes for cleaning, and then bubble and rotate for 35 minutes for cleaning. Step 4. Place the cleaned denitrification catalyst crushed material into pure water for bubble washing; Step 5. Prepare an acid washing solution by mixing sulfuric acid and oxalic acid. Put the crushed denitrification catalyst into the acid washing solution and let it stand for 35 minutes at room temperature. Then, bubble and rotate the solution for 30 minutes. Step 6. Rinse the crushed denitrification catalyst material in pure water and then remove it.
2. The method for porous cleaning of crushed material based on denitrification catalyst according to claim 1, characterized in that, In step 2, the first bubbling rinse lasts for 25 minutes, and the second bubbling rinse lasts for 15 minutes.
3. The method for porous cleaning of crushed material based on denitrification catalyst according to claim 1, characterized in that, In step 3, the concentration of sodium hydroxide solution is 0.5%-1%.
4. The method for porous cleaning of crushed material based on denitrification catalyst according to claim 1, characterized in that, The concentration of sulfuric acid in the pickling solution is 0.05 mol / L, and the concentration of oxalic acid in the pickling solution is 0.02 mol / L.