In-situ regeneration device for hydrogen peroxide palladium catalyst by anthraquinone process
The in-situ regeneration device for palladium peroxide catalyst via the anthraquinone process utilizes solvents under negative pressure and bubbling to clean impurities from the catalyst surface, thus solving the problem of palladium catalyst deactivation and achieving efficient regeneration and improved production efficiency.
Patent Information
- Application Number
- CN202520100644.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Utility models(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-16
- Publication Date
- 2026-01-23
- Estimated Expiration
- 2035-01-16
AI Technical Summary
Existing technologies cannot effectively and completely remove harmful substances from the active pores of palladium catalysts, leading to catalyst deactivation and long regeneration time, which reduces production efficiency.
An in-situ regeneration device for palladium peroxide catalyst using the anthraquinone method is employed. Solvents such as ethanol, acetic acid, hot ionized water, and soft water are used to clean impurities on the catalyst surface under negative pressure and bubbling action. Efficient regeneration is achieved through a purge pipe and a closed pipeline.
It significantly improves solvent soaking and rinsing efficiency, shortens regeneration time, restores catalyst activity, and increases hydrogen peroxide production efficiency.
Smart Images
Figure CN223818692U_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The utility model relates to the field of catalyst regeneration, and specifically provides an anthraquinone hydrogen peroxide palladium catalyst in-situ regeneration device. BACKGROUND
[0002] The mainstream process for domestic H2O2 production is the anthraquinone hydrogen peroxide technology using a palladium catalyst fixed bed, which has the advantages of high hydrogenation activity, small dosage, easy regeneration, long service life, etc. In industrial production, the release period of the hydrogenation activity of the palladium catalyst is 6-12 months. With the extension of time, the hydrogenation activity of the palladium catalyst gradually decreases. When the hydrogenation activity of the palladium catalyst cannot meet the production requirements, it is called "deactivation" of the palladium catalyst.
[0003] At present, the "deactivation" of the palladium catalyst mainly uses steam purging regeneration method, solvent washing regeneration method, high-temperature regeneration method, and oxidation liquid regeneration method. These methods cannot effectively and completely remove harmful substances adhering to the active channels of the catalyst in actual application. After regeneration, the service period is generally 3-6 months, and the regeneration time is relatively long, which greatly reduces the production efficiency. SUMMARY
[0004] The utility model provides an anthraquinone hydrogen peroxide palladium catalyst in-situ regeneration device aiming at the deficiencies of the prior art.
[0005] The utility model solves the technical scheme that the utility model discloses an anthraquinone hydrogen peroxide palladium catalyst in-situ regeneration device, which comprises an in-situ regeneration hydrogenation tower,
[0006] The in-situ regeneration hydrogenation tower is internally provided with a purging unit, the purging unit is connected with a tower-external steam pipeline and a nitrogen pipeline through an air inlet,
[0007] The in-situ regeneration hydrogenation tower is provided with a soaking liquid inlet and a waste liquid outlet, the soaking liquid inlet is connected with an ethanol tank, an acetic acid tank, a hot ion water tank and a soft water tank,
[0008] The in-situ regeneration hydrogenation tower is provided with a vacuum extraction pipe opening, which is connected with a vacuum extraction system.
[0009] As a preferred, the high-efficiency regeneration device further comprises a bubbling closed pipeline arranged outside the in-situ regeneration hydrogenation tower, and the bubbling closed pipeline forms a closed pipeline with the purging unit.
[0010] As a preferred, the purging unit is composed of a purging pipe, an air inlet manifold and an air outlet manifold, 4-20 purging pipes are arranged in the catalyst bed layer of the in-situ regeneration hydrogenation tower and are connected with the purging unit air inlet and the purging unit air outlet of the in-situ regeneration hydrogenation tower through the air inlet manifold and the air outlet manifold.
[0011] Preferably, 4 to 20 purge pipes are vertically arranged in the catalyst bed of the in-situ regeneration hydrogenation tower, with the purge height being consistent with the height of the catalyst bed.
[0012] Preferably, the inner diameter of the purge tube is φ1 = 20-50 cm, the diameter of the purge holes on the tube wall is φ2 = 0.5-1.5 cm, and the spacing between adjacent holes is 1.5-3 cm (along the axial direction of the purge tube).
[0013] Preferably, the purge tube consists of a central tube and an outer tube, wherein the diameter of the purge hole on the central tube is larger than the diameter of the purge hole on the outer tube.
[0014] Preferably, the purge tube is wrapped with a stainless steel wire mesh with a mesh size of 80–150 μm.
[0015] Preferably, the bubbling sealed pipeline is connected to the external steam pipeline and nitrogen pipeline.
[0016] As a preferred option, both the steam pipeline and the nitrogen pipeline outside the tower are equipped with flow control valves.
[0017] Compared with existing technologies, the anthraquinone method palladium peroxide catalyst in-situ regeneration device of this invention has the following outstanding advantages:
[0018] (i) Ethanol, acetic acid, thermal ionization water tank or soft water can be introduced into the in-situ regeneration hydrogenation tower as needed. Thermal ionization water is used to activate and clean the catalyst surface of easily soluble substances such as carbonates and phosphates; dilute acetic acid is used to acidify the sparingly soluble aluminum molecules attached to the active center of the catalyst to restore the active channels of the catalyst molecular sieve; ethanol solution is used to dissolve organic solvents such as acetic acid, octyl phosphate, anthraquinone, and hydroanthraquinone that are attached to the active center of the catalyst; and soft water is used to soak and rinse to thoroughly remove all inorganic and organic impurities from the palladium catalyst.
[0019] (ii) The soaking and rinsing process can be completed under negative pressure and bubbling, which significantly improves the efficiency of solvent soaking and rinsing, reduces the amount of solvent used and the soaking time, thereby greatly shortening the regeneration time;
[0020] (iii) In-situ regeneration can be achieved, the catalyst does not need to be removed from the reactor, which can further shorten the regeneration time and improve the hydrogen peroxide production efficiency. Attached Figure Description
[0021] Appendix Figure 1 This is a schematic diagram of the in-situ regeneration hydrogenation tower structure in Example 1;
[0022] Appendix Figure 2 yes Figure 1 A schematic diagram of the AA cross-sectional structure of the in-situ regeneration hydrogenation tower shown.
[0023] Appendix Figure 3 yesFigure 1 Schematic diagram of the BB cross-sectional structure of the in-situ regeneration hydrogenation tower shown;
[0024] Appendix Figure 4 yes Figure 1 The diagram shows the structure of the purge pipe for the in-situ regeneration hydrogenation tower.
[0025] Appendix Figure 5 This is a schematic diagram of the in-situ regeneration device for palladium hydrogen peroxide catalyst in the anthraquinone process, as shown in Example 2.
[0026] 1. In-situ regeneration hydrogenation tower; 11. Purge unit inlet; 12. Purge unit outlet; 13. Vacuum pump port; 14. Immersion solution inlet; 15. Waste liquid outlet.
[0027] 2. Purge unit, 21. Purge pipe, 22. Purge port, 23. Wire mesh, 24. Main inlet pipe, 25. Main outlet pipe
[0028] 3. Bubble-sealed pipeline,
[0029] 4. Vacuum system,
[0030] 51. Ethanol tank, 52. Acetic acid tank, 53. Thermo-ionized water tank, 54. Soft water tank, 55. Centrifugal pump, 56. Waste liquid tank,
[0031] 61. Steam pipeline, 62. Nitrogen pipeline. Detailed Implementation
[0032] The present invention will be further described below with reference to specific embodiments, but this is not intended to limit the present invention.
[0033] Example 1
[0034] An in-situ regeneration hydrogenation tower 1 has the same basic structure as conventional hydrogenation towers in the prior art, and a catalyst layer is provided inside the tower.
[0035] As attached Figures 1-4 As shown, the in-situ regeneration hydrogenation tower 1 of this embodiment is equipped with a purging unit 2. The purging unit 2 consists of a purging pipe 21, an inlet manifold 24, and an outlet manifold 25. The lower end of the purging pipe 21 is connected to the inlet 11 of the purging unit of the in-situ regeneration hydrogenation tower 1 through the inlet manifold 24, and the upper end is connected to the outlet 12 of the purging unit of the in-situ regeneration hydrogenation tower 1 through the outlet manifold 25.
[0036] To ensure uniform distribution of the purge gas, eight purge pipes 21 are vertically arranged in the catalyst bed of the in-situ regeneration hydrogenation tower 1. The inner diameter of each purge pipe 21 is φ1 = 30 cm, its length is 8 m, and its purging height is the same as the height of the catalyst bed. A purge hole 22 with a diameter of φ2 = 1.2 cm is opened on the purge pipe 21 at the axial position, while the other purge pipes 21 have purge holes 22 with a diameter of φ2 = 0.8 cm. The purge holes 22 are evenly spaced 2.6 cm apart along the axial direction of the purge pipe 21.
[0037] The purge tube 21 is wrapped with 100μm 316 steel wire mesh 23 and inserted into the catalyst bed.
[0038] Example 2
[0039] The structure of the in-situ regeneration hydrogenation tower 1 in this embodiment is basically the same as that in Embodiment 1, except that the catalyst bed is provided with 12 purge pipes 21. The inner diameter of the purge pipe 21 is φ1 = 30cm, the length is 8m, the diameter of the purge hole 22 on the pipe wall is φ2 = 1.0cm, and the purge holes 22 are arranged at equal intervals of 2.5cm along the axial direction of the purge pipe 21.
[0040] Example 3
[0041] As attached Figure 5 As shown, the in-situ regeneration device for palladium peroxide catalyst in the anthraquinone process includes the in-situ regeneration hydrogenation tower 1, the bubbling sealed pipeline 3, the vacuum system 4, the ethanol tank 51, the acetic acid tank 52, the thermal ionization water tank 53, the soft water tank 54, the centrifugal pump 55, and the waste liquid tank 56 described in Example 1.
[0042] The bubbling closed pipeline 3 is connected to the air inlet 11 and air outlet 12 of the purging unit of the in-situ regeneration hydrogenation tower 1, forming a closed pipeline with the purging unit 2, and is connected to the external steam pipeline 61 and nitrogen pipeline 62. Both the steam pipeline 61 and the nitrogen pipeline 62 are equipped with flow control valves.
[0043] The vacuum system 4 is connected to the vacuum port 13 of the in-situ regeneration hydrogenation tower 1.
[0044] Ethanol tank 51, acetic acid tank 52, thermal ionization water tank 53, and soft water tank 54 are all connected to the soaking liquid inlet 14 at the top of the in-situ regeneration hydrogenation tower 1 via centrifugal pump 55, and waste liquid outlet 15 at the bottom of the in-situ regeneration hydrogenation tower 1 is connected to waste liquid tank 56.
[0045] During normal production (hydrogen peroxide production via the anthraquinone method using palladium catalyst) of the in-situ regeneration hydrogenation tower 1, blind flanges are installed on the valves of the purge unit inlet 11 and outlet 12 to isolate them from the hydrogen peroxide system. When the catalyst is reduced, the blind flanges are removed, and the regeneration device is integrated into the system. Ethanol, acetic acid, hot ionized water, and soft water can be pumped into the catalyst bed of the in-situ regeneration hydrogenation tower 1 via centrifugal pump 55 to soak the catalyst. The soaked solvent enters the waste liquid tank 56 and is then sent to the oxidizer for incineration. A vacuum system 4 can be used to create a certain negative pressure inside the tower, increasing the soaking depth. Steam and nitrogen used for bubbling and purging enter through steam pipeline 61 and nitrogen pipeline 62, respectively, forming closed pipelines. Appropriate replenishment of steam / nitrogen maintains the required vacuum level in the system.
[0046] The above embodiments and comparative examples are only the optimal cases selected under all conditions and do not represent all cases. All research and explorations conducted based on parallel variations of all data and conditions in this invention are within the scope of protection.
Claims
1. An in-situ regeneration device for palladium hydrogen peroxide catalyst in the anthraquinone process, characterized in that: Including in-situ regeneration hydrogenation tower, The in-situ regeneration hydrogenation tower is equipped with a purging unit, the inlet of which is connected to the external steam and nitrogen pipelines. The in-situ regeneration hydrogenation tower is equipped with a soaking solution inlet and a waste liquid outlet. The soaking solution inlet connects to an ethanol tank, an acetic acid tank, a thermal ionization water tank, and a soft water tank. The in-situ regeneration hydrogenation tower is equipped with a vacuum port, which is connected to the vacuum system.
2. The anthraquinone process palladium peroxide catalyst in-situ regeneration device according to claim 1, characterized in that, The in-situ regeneration device also includes a bubbling closed pipeline located outside the in-situ regeneration hydrogenation tower, which forms a closed pipeline with the purging unit.
3. The in-situ regeneration device for palladium hydrogen peroxide catalyst in the anthraquinone process according to claim 1 or 2, characterized in that, The purging unit consists of purging pipes, an inlet manifold, and an outlet manifold. 4 to 20 purging pipes are arranged in the catalyst bed of the in-situ regeneration hydrogenation tower and are connected to the inlet and outlet of the purging unit of the in-situ regeneration hydrogenation tower through the inlet manifold and outlet manifold.
4. The anthraquinone process palladium peroxide catalyst in-situ regeneration device according to claim 3, characterized in that, Four to twenty purge pipes are vertically arranged in the catalyst bed of the in-situ regeneration hydrogenation tower, with the purge height being consistent with the height of the catalyst bed.
5. The anthraquinone process palladium peroxide catalyst in-situ regeneration device according to claim 3, characterized in that, The inner diameter of the purge tube is φ1 = 20-50cm, the diameter of the purge holes on the tube wall is φ2 = 0.5-1.5cm, and the distance between adjacent holes is 1.5-3cm.
6. The anthraquinone process palladium peroxide catalyst in-situ regeneration device according to claim 5, characterized in that, The purge tube consists of a central tube and an outer tube, with the diameter of the purge hole on the central tube being larger than the diameter of the purge hole on the outer tube.
7. The anthraquinone process palladium peroxide catalyst in-situ regeneration device according to claim 3, characterized in that, The purge tube is wrapped with a stainless steel wire mesh with a mesh size of 80–150 μm.
8. The in-situ regeneration device for palladium hydrogen peroxide catalyst in the anthraquinone process according to claim 2, characterized in that, The bubbling sealed pipeline is connected to the external steam pipeline and nitrogen pipeline.
9. The in-situ regeneration device for palladium hydrogen peroxide catalyst in the anthraquinone process according to claim 2, characterized in that, Flow control valves are installed on both the steam pipeline and the nitrogen pipeline outside the tower.