A method for regenerating an alkylation catalyst
Patent Information
- Application Number
- CN202611109019.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-07-24
- Publication Date
- 2026-10-20
AI Technical Summary
[0004]然而，现有的烷基催化剂的再生性能有限：积碳是烷基催化剂的主要失活原因
本发明提供的烷基化催化剂的再生方法，超声的物理振动和空化效应持续冲刷催化剂表面，既帮助去除O3氧化后的积碳残渣，又将新的深层积碳暴露在O3氛围；而O3在超声辅助下快速分解，将积碳氧化为CO2和H2O。脉冲超声-臭氧协同对烷基化催化剂进行再生，提高了催化剂的再生速率和再生效果。
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of alkyl catalyst regeneration technology, and specifically relates to a method for regenerating alkylation catalysts. Background Technology
[0002] Alkylation catalysts are substances that, in alkylation reactions, promote the transfer of alkyl groups (such as methyl, ethyl, long-chain alkyl, etc.) from one molecule to another molecule (usually aromatic hydrocarbons, such as benzene, toluene), thereby generating alkylation products.
[0003] Existing alkyl catalysts mainly include liquid acid catalysts (such as concentrated sulfuric acid, phosphoric acid, Lewis acids, chloroaluminate ionic liquids, etc.), molecular sieve catalysts (such as ZSM-5, Y-type, β-type), supported catalysts (such as AlCl3 supported catalysts: AlCl3 supported on SiO2, Al2O3, etc.), cation exchange resins (such as sulfonated polystyrene-divinylbenzene copolymer), and solid phosphoric acid catalysts (such as phosphoric acid supported on diatomaceous earth, silica gel, or zeolite).
[0004] However, the regeneration performance of existing alkyl catalysts is limited: carbon deposition is the main cause of deactivation of alkyl catalysts. Existing catalysts (such as AlCl3 supported on molecular sieves) require high-temperature carbonization for regeneration, but this process easily leads to skeleton dealumination or sintering of active components, resulting in a significant decrease in specific surface area and acid content, and a low number of regeneration cycles (usually ≤5 times), making them uneconomical. Summary of the Invention
[0005] To address the aforementioned problems, the present invention provides a method for regenerating an alkylation catalyst, thereby resolving at least one aspect of the above-mentioned technical problems.
[0006] This invention is achieved through the following technical solution: This invention provides a method for regenerating an alkylation catalyst, comprising the following steps: The alkylation catalyst was subjected to pulsed ultrasound-ozone synergistic treatment. The duration of the pulse ultrasound working period is 4s to 6s, and the duration of the rest period is 4s to 6s.
[0007] In some possible implementations, the pulsed ultrasound-ozone synergistic treatment includes the following steps: The alkylation catalyst and regeneration medium are mixed and treated under pulsed ultrasound.
[0008] In some possible implementations, the frequency of the pulsed ultrasound is 25 kHz to 40 kHz.
[0009] In some possible implementations, the power per unit volume of the pulsed ultrasound is 50W / L to 100W / L.
[0010] In some possible implementations, the regeneration medium comprises a mixture of ozone and nitrogen.
[0011] In some possible implementations, the ozone volume concentration in the mixture is 5% to 10%.
[0012] In some possible implementations, the flow rate of the regeneration medium is 150 ml / min to 250 ml / min.
[0013] In some possible implementations, the alkylation catalyst includes at least one of ZSM-5 molecular sieve and BEA molecular sieve.
[0014] In some possible implementations, the temperature at which the alkylation catalyst and the regeneration medium are mixed is 120°C to 150°C.
[0015] In some possible implementations, the alkylation catalyst and the regeneration medium are mixed for 2 to 4 hours.
[0016] In some possible implementations, the regeneration method further includes a post-processing step: After the pulsed ultrasound-ozone synergistic treatment, a metal thin film is deposited on the surface of the alkylation catalyst using atomic layer deposition.
[0017] The alkylation catalyst regeneration method provided by this invention has at least the following beneficial technical effects compared with the prior art: The regeneration method for alkylation catalysts provided by this invention utilizes the physical vibration and cavitation effect of ultrasound to continuously scour the catalyst surface. This helps remove carbon deposits after O3 oxidation and exposes new, deeper carbon deposits to the O3 atmosphere. Furthermore, O3 rapidly decomposes under ultrasonic assistance, oxidizing the carbon deposits into CO2 and H2O. The synergistic regeneration of the alkylation catalyst using pulsed ultrasound and ozone improves both the regeneration rate and the regeneration effect. Detailed Implementation
[0018] To make the objectives, technical solutions, and advantages of this invention clearer, the invention is described and illustrated below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention. All other embodiments obtained by those skilled in the art based on the embodiments provided by this invention without inventive effort are within the scope of protection of this invention.
[0019] Obviously, the following description is merely some examples or embodiments of the present invention. Those skilled in the art can apply the present invention to other similar scenarios without any inventive effort. Furthermore, it is understood that although the effort involved in such development may be complex and lengthy, for those skilled in the art related to the content disclosed in this invention, modifications to design, manufacturing, or production based on the technical content disclosed in this invention are merely conventional technical means and should not be construed as insufficient disclosure of the present invention.
[0020] However, there may be instances where unnecessary detailed descriptions are omitted. For example, detailed descriptions of well-known matters or repetitive descriptions of essentially the same structures may be omitted. This is to avoid making the following description unnecessarily lengthy and to facilitate understanding by those skilled in the art. Furthermore, the following description is provided to enable those skilled in the art to fully understand the invention and is not intended to limit the subject matter of the claims.
[0021] Unless otherwise specified, all embodiments and optional embodiments of the present invention can be combined with each other to form new technical solutions, and all technical features and optional technical features of the present invention can be combined with each other to form new technical solutions.
[0022] This invention provides a method for regenerating an alkylation catalyst, comprising the following steps: S10. The alkylation catalyst is subjected to pulsed ultrasound-ozone synergistic treatment; The duration of the pulse ultrasound working period is 4s to 6s, and the duration of the rest period is 4s to 6s.
[0023] The alkylation catalyst regeneration method provided in this invention utilizes the physical vibration and cavitation effect of ultrasound to continuously scour the catalyst surface. This helps remove carbon deposits after O3 oxidation and exposes new, deeper carbon deposits to the O3 atmosphere. Furthermore, O3 rapidly decomposes under ultrasonic assistance, oxidizing the carbon deposits into CO2 and H2O. This pulsed ultrasound-ozone synergistic treatment for alkylation catalyst regeneration improves the regeneration rate and efficiency.
[0024] In some embodiments, in step S10 above, the alkylation catalyst includes at least one of ZSM-5 molecular sieve and BEA molecular sieve.
[0025] In some embodiments, the ZSM-5 molecular sieve includes at least one of H-ZSM-5, Ni / HZSM-5, and Pt / HZSM-5.
[0026] In some embodiments, the silica-alumina ratio of ZSM-5 molecular sieve is 38~200.
[0027] In some specific embodiments, the silica-alumina ratio of the ZSM-5 molecular sieve is 38~160.
[0028] In some specific embodiments, the silica-alumina ratio of ZSM-5 molecular sieve is 160~200.
[0029] In some embodiments, BEA molecular sieves include at least one of NKF-6-25H, NKF-6-30H, NKF-6-40H, NKF-6-60H, and NKF-6-100H.
[0030] In some embodiments, the silica-to-alumina ratio of BEA molecular sieves is 26 to 150.
[0031] In some specific embodiments, the silica-to-alumina ratio of the BEA molecular sieve is 26 to 102.
[0032] In some specific embodiments, the silica-to-alumina ratio of the BEA molecular sieve is 102 to 150.
[0033] In some embodiments, in step S10 above, the pulsed ultrasound-ozone synergistic treatment includes the following steps: S101. The alkylation catalyst and regeneration medium are mixed and treated under pulsed ultrasound.
[0034] In some embodiments, in step S101 above, the frequency of the pulsed ultrasound is 25 kHz to 40 kHz. In this case, the low-frequency ultrasound can generate a strong cavitation effect, thereby efficiently removing the carbon deposits after O3 oxidation on the surface of the alkylation catalyst, and exposing new deep carbon deposits to the O3 atmosphere.
[0035] In some embodiments, in step S101 above, the volumetric power of the pulsed ultrasound is 50W / L to 100W / L.
[0036] In some embodiments, in step S101 described above, the regeneration medium includes a mixture of ozone and nitrogen.
[0037] In some embodiments, the volume concentration of ozone in the gas mixture is 5% to 10%.
[0038] In some embodiments, in step S101 above, the flow rate of the regeneration medium is 150 ml / min to 250 ml / min.
[0039] In some embodiments, in step S101 above, the temperature at which the alkylation catalyst and the regeneration medium are mixed is 120°C to 150°C.
[0040] In some embodiments, in step S101 above, the mixing time of the alkylation catalyst and the regeneration medium is 2h to 4h.
[0041] In some embodiments, a method for regenerating an alkylation catalyst is provided, further comprising the following steps: S20. The alkylation catalyst, after being treated with pulsed ultrasound and ozone in synergy, is activated by purging with inert gas.
[0042] In this case, residual carbon deposits, O3 and other impurities are purged to ensure that the catalyst is clean and dry before use; activation restores the activity of acidic sites on the alkylation catalyst.
[0043] In some embodiments, the inert gas in step S20 described above includes nitrogen or argon.
[0044] In some embodiments, in step S20 above, the flow rate of the inert gas used for purging is 80 ml / min to 120 ml / min.
[0045] In some embodiments, in step S20 above, the inert gas purging time is 30 min to 50 min.
[0046] In some embodiments, in step S20 above, activation includes the following steps: S201. Dry the alkylation catalyst to constant weight under an inert atmosphere.
[0047] In some embodiments, in step S201 above, the temperature of the inert atmosphere is 110°C to 120°C.
[0048] In some embodiments, in step S201 above, the flow rate of the inert atmosphere is 100 ml / min to 120 ml / min.
[0049] In some embodiments, a method for regenerating an alkylation catalyst is provided, further comprising the following steps: S20. After pulsed ultrasound-ozone synergistic treatment, a metal film is deposited on the surface of the alkylation catalyst using atomic layer deposition.
[0050] In this case, depositing a metal film on the surface of the alkylation catalyst not only improves the catalyst's catalytic performance, but also enhances the catalyst's resistance to carbon deposition.
[0051] In some embodiments, in step S20 above, depositing a metal thin film on the surface of the alkylation catalyst using atomic layer deposition (ALD) includes the following steps: S201. After fluorinating the alkylation catalyst, an atomic layer deposition of a metal thin film is performed.
[0052] In some embodiments, in step S201 above, the fluorination treatment includes the following steps: S2011. Fluoride the alkylation catalyst under a fluorine-containing atmosphere.
[0053] In some embodiments, in step S2011 above, the fluorine-containing atmosphere includes one of carbon tetrafluoride and trifluoromethane.
[0054] In some embodiments, in step S2011 above, the fluorination temperature is 300°C to 500°C.
[0055] In some embodiments, in step S2011 above, the fluorination time is 3h to 5h.
[0056] In some embodiments, in step S201 above, the metal of the metal thin film includes at least one of molybdenum (Mo) and nickel (Ni).
[0057] In some embodiments, the molybdenum (Mo) deposition precursor includes molybdenum dichloride (MoCl2O2).
[0058] In some embodiments, the nickel (Ni) deposition precursor comprises nickel dicerocene [Ni(Cp)2].
[0059] In some embodiments, in step S201 above, atomic layer deposition is plasma-enhanced atomic layer deposition.
[0060] In some embodiments, in step S201 above, atomic layer deposition includes the following steps: S2012. After depositing a metal precursor on the surface of an alkylation catalyst, the metal precursor is reduced under a reducing atmosphere.
[0061] In some embodiments, in step S2012 above, the reducing atmosphere includes hydrogen.
[0062] In some embodiments, in step S2012 above, the reduction temperature is 300°C to 500°C.
[0063] The following description, in conjunction with specific embodiments, provides further details.
[0064] Example 1 Example 1 provides a method for regenerating an alkylation catalyst, comprising the following steps: E10. Pulsed ultrasound-ozone synergistic treatment The alkylation catalyst and regeneration medium are mixed and treated under pulsed ultrasound.
[0065] The alkylation catalyst is H-ZSM-5 molecular sieve with a silicon-to-aluminum ratio of 160.
[0066] The pulse ultrasound has a frequency of 30kHz, a working period duration of 5s, a rest period duration of 5s, and a power per unit volume of 85W / L.
[0067] The regeneration medium is a mixture of ozone and nitrogen, with an ozone volume concentration of 8%; the flow rate of the regeneration medium is 200 ml / min.
[0068] The alkylation catalyst and regeneration medium were mixed at a temperature of 140°C for 3 hours.
[0069] E20. Purge Nitrogen gas is used to purge the alkylation catalyst, which has been treated with pulsed ultrasound and ozone.
[0070] The nitrogen purging flow rate was 100 ml / min and the purging time was 40 min.
[0071] E30. Activation The alkylation catalyst was dried to constant weight under a nitrogen atmosphere.
[0072] The nitrogen atmosphere was set at a temperature of 110℃ and a flow rate of 100 ml / min.
[0073] E40. Fluorination treatment The alkylation catalyst is fluorinated in a carbon tetrafluoride atmosphere.
[0074] The fluorination process involves a temperature of 400℃ and a time of 4 hours.
[0075] E50. Plasma-enhanced atomic layer deposition After depositing a metal precursor on the surface of the alkylation catalyst, the metal precursor is reduced under a hydrogen atmosphere to obtain a regenerated alkylation catalyst containing a molybdenum metal film.
[0076] The deposition precursor for the molybdenum metal thin film is molybdenum dioxide dichloride, with a reduction temperature of 400℃.
[0077] Example 2 Example 2 provides a method for regenerating an alkylation catalyst, the steps of which are as follows: E11. Pulsed ultrasound-ozone synergistic treatment The alkylation catalyst and regeneration medium are mixed and treated under pulsed ultrasound.
[0078] The alkylation catalyst is H-ZSM-5 molecular sieve with a silicon-to-aluminum ratio of 38.
[0079] The pulse ultrasound has a frequency of 25kHz, a working period duration of 4s, a rest period duration of 4s, and a power per unit volume of 50W / L.
[0080] The regeneration medium is a mixture of ozone and nitrogen, with an ozone volume concentration of 5%; the flow rate of the regeneration medium is 150 ml / min.
[0081] The alkylation catalyst and regeneration medium were mixed at a temperature of 120°C for 4 hours.
[0082] E21. Purge Nitrogen gas is used to purge the alkylation catalyst, which has been treated with pulsed ultrasound and ozone.
[0083] The nitrogen purging flow rate was 100 ml / min and the purging time was 40 min.
[0084] E31. Activation The alkylation catalyst was dried to constant weight under a nitrogen atmosphere.
[0085] The nitrogen atmosphere was set at a temperature of 110℃ and a flow rate of 100 ml / min.
[0086] Example 3 Example 3 provides a method for regenerating an alkylation catalyst, the steps of which are as follows: E12. Pulsed ultrasound-ozone synergistic treatment The alkylation catalyst and regeneration medium are mixed and treated under pulsed ultrasound.
[0087] The alkylation catalyst is H-ZSM-5 molecular sieve with a silicon-to-aluminum ratio of 200.
[0088] The pulse ultrasound has a frequency of 40kHz, a working period duration of 6s, a rest period duration of 6s, and a power per unit volume of 100W / L.
[0089] The regeneration medium is a mixture of ozone and nitrogen, with an ozone volume concentration of 10%; the flow rate of the regeneration medium is 250 ml / min.
[0090] The alkylation catalyst and regeneration medium were mixed at a temperature of 150°C for 2 hours.
[0091] E22. Purge Nitrogen gas is used to purge the alkylation catalyst, which has been treated with pulsed ultrasound and ozone.
[0092] The nitrogen purging flow rate was 100 ml / min and the purging time was 40 min.
[0093] E32. Activation The alkylation catalyst was dried to constant weight under a nitrogen atmosphere.
[0094] The nitrogen atmosphere was set at a temperature of 110℃ and a flow rate of 100 ml / min.
[0095] E42. Fluorination treatment The alkylation catalyst is fluorinated in a carbon tetrafluoride atmosphere.
[0096] The fluorination process involves a temperature of 500℃ and a time of 4 hours.
[0097] E52. Plasma-enhanced atomic layer deposition After depositing a metal precursor on the surface of the alkylation catalyst, the metal precursor is reduced under a hydrogen atmosphere to obtain a regenerated nickel-containing metal film alkylation catalyst.
[0098] The metal precursor is nickel dicene, and the reduction temperature is 400℃.
[0099] Example 4 Example 4 provides a method for regenerating an alkylation catalyst, the steps of which are basically the same as those in Example 1, except that: In step E10, the alkylation catalyst is NKF-6-100H, and the silicon-to-aluminum ratio is 102.
[0100] Comparative Example 1 Comparative Example 1 provides a method for regenerating an alkylation catalyst, comprising the following steps: D10. Pulsed ultrasound treatment The alkylation catalyst and regeneration medium are mixed and treated under pulsed ultrasound.
[0101] The alkylation catalyst is H-ZSM-5 molecular sieve with a silicon-to-aluminum ratio of 160.
[0102] The pulse ultrasound has a frequency of 30kHz, a working period duration of 5s, a rest period duration of 5s, and a power per unit volume of 85W / L.
[0103] The regeneration medium is a mixture of ozone and nitrogen, with an ozone volume concentration of 8%; the flow rate of the regeneration medium is 200 ml / min.
[0104] The alkylation catalyst and regeneration medium were mixed at a temperature of 140°C for 3 hours.
[0105] D20. Purge Nitrogen gas is used to purge the alkylation catalyst, which has been treated with pulsed ultrasound and ozone.
[0106] The nitrogen purging flow rate was 100 ml / min and the purging time was 40 min.
[0107] D30. Activation The alkylation catalyst was dried to constant weight under a nitrogen atmosphere.
[0108] The nitrogen atmosphere was set at a temperature of 110℃ and a flow rate of 100 ml / min.
[0109] D40. Plasma-enhanced atomic layer deposition After depositing a metal precursor on the surface of the alkylation catalyst, the metal precursor is reduced under a hydrogen atmosphere to obtain a regenerated alkylation catalyst containing a molybdenum metal film.
[0110] The deposition precursor for the molybdenum metal thin film is molybdenum dioxide dichloride, with a reduction temperature of 400℃.
[0111] Comparative Example 2 Comparative Example 2 provides a method for regenerating an alkylation catalyst, comprising the following steps: D11. Ozone Treatment The alkylation catalyst and regeneration medium are mixed and treated.
[0112] The alkylation catalyst is H-ZSM-5 molecular sieve with a silicon-to-aluminum ratio of 160.
[0113] The regeneration medium is a mixture of ozone and nitrogen, with an ozone volume concentration of 8%; the flow rate of the regeneration medium is 200 ml / min.
[0114] The alkylation catalyst and regeneration medium were mixed at a temperature of 140°C for 3 hours.
[0115] D21. Purge Nitrogen gas is used to purge the alkylation catalyst, which has been treated with pulsed ultrasound and ozone.
[0116] The nitrogen purging flow rate was 100 ml / min and the purging time was 40 min.
[0117] D31. Activation The alkylation catalyst was dried to constant weight under a nitrogen atmosphere.
[0118] The nitrogen atmosphere was set at a temperature of 110℃ and a flow rate of 100 ml / min.
[0119] To verify the advancement of the alkylation catalyst regeneration method provided in this embodiment of the invention, the specific surface area and pore volume of the regenerated alkylation catalysts obtained by the regeneration methods of the embodiments and comparative examples of this invention were measured, and the results are shown in Table 1 below. Furthermore, the regenerated alkylation catalyst was used in a catalytic reaction, and the average carbon deposition rate (wt% / h) of the regenerated catalyst was measured.
[0120] Table 1
[0121] From Table 1 above, at least the following conclusions can be drawn: (1) Comparative Example 1 used only pulsed ultrasound treatment, and Comparative Example 2 used only ozone treatment. The specific surface area and pore volume of the regenerated alkylation catalyst were both lower than those of the examples. Therefore, the alkylation catalyst regeneration method provided by the embodiments of the present invention utilizes the physical vibration and cavitation effect of ultrasound to continuously scour the catalyst surface, helping to remove carbon deposits after O3 oxidation and exposing new deep carbon deposits to the O3 atmosphere. O3 decomposes rapidly under the assistance of ultrasound, oxidizing the carbon deposits into CO2 and H2O. The synergistic regeneration of the alkylation catalyst using pulsed ultrasound and ozone maximizes the specific surface area of the regenerated catalyst, thereby improving the regeneration efficiency and effect, and ultimately extending the catalyst's service life.
[0122] (2) In Example 1, a metal film was deposited on the surface of the activated catalyst. Compared with Example 2, where no metal film was deposited, the average carbon deposition rate was significantly reduced. Similarly, in Comparative Examples 1 and 2, the average carbon deposition rate of Comparative Example 1 was also significantly lower than that of Comparative Example 2. Therefore, the alkylation catalyst regeneration method provided by the embodiments of the present invention can effectively prevent the accumulation of high-molecular-weight organic carbon during subsequent catalyst use, as severe carbon deposition can negatively impact the catalytic performance of the catalyst.
[0123] It should be noted that the present invention is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments that have the same structure and perform the same effects as the technical concept within the scope of the present invention are included within the scope of the present invention. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of the present invention, are also included within the scope of the present invention.
Claims
1. A method for regenerating an alkylation catalyst, characterized in that, Includes the following steps: The alkylation catalyst was subjected to pulsed ultrasound-ozone synergistic treatment. The duration of the pulse ultrasound working period is 4s to 6s, and the duration of the rest period is 4s to 6s.
2. The method for regenerating the alkylation catalyst according to claim 1, characterized in that, The pulsed ultrasound-ozone synergistic treatment includes the following steps: The alkylation catalyst and regeneration medium are mixed and treated under pulsed ultrasound.
3. The method for regenerating the alkylation catalyst according to claim 2, characterized in that, The frequency of the pulsed ultrasound is 25kHz~40kHz.
4. The method for regenerating the alkylation catalyst according to claim 2, characterized in that, The power per unit volume of the pulsed ultrasound is 50W / L~100W / L.
5. The method for regenerating the alkylation catalyst according to claim 2, characterized in that, The regeneration medium comprises a mixture of ozone and nitrogen.
6. The method for regenerating the alkylation catalyst according to claim 5, characterized in that, The ozone volume concentration in the mixture is 5% to 10%.
7. The method for regenerating the alkylation catalyst according to claim 2, characterized in that, The flow rate of the regeneration medium is 150 ml / min to 250 ml / min.
8. The method for regenerating the alkylation catalyst according to claim 1, characterized in that, The alkylation catalyst includes at least one of ZSM-5 molecular sieve and BEA molecular sieve.
9. The method for regenerating the alkylation catalyst according to claim 2, characterized in that, It satisfies at least one of the following characteristics (1) to (2): (1) The mixing temperature of the alkylation catalyst and the regeneration medium is 120℃~150℃; (2) The mixing time of the alkylation catalyst and the regeneration medium is 2h~4h.
10. The method for regenerating the alkylation catalyst according to any one of claims 1 to 9, characterized in that, The regeneration method further includes a post-processing step: After the pulsed ultrasound-ozone synergistic treatment, a metal thin film is deposited on the surface of the alkylation catalyst using atomic layer deposition.