CN115845933A - Regeneration method of molecular sieve catalyst - Google Patents
Regeneration method of molecular sieve catalyst Download PDFInfo
- Publication number
- CN115845933A CN115845933A CN202211428228.1A CN202211428228A CN115845933A CN 115845933 A CN115845933 A CN 115845933A CN 202211428228 A CN202211428228 A CN 202211428228A CN 115845933 A CN115845933 A CN 115845933A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- sieve catalyst
- inert gas
- purging
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 217
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 138
- 238000011069 regeneration method Methods 0.000 title claims abstract description 41
- 238000010926 purge Methods 0.000 claims abstract description 118
- 239000011261 inert gas Substances 0.000 claims abstract description 72
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000001257 hydrogen Substances 0.000 claims abstract description 58
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 58
- 239000012159 carrier gas Substances 0.000 claims abstract description 32
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 25
- 238000011065 in-situ storage Methods 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 45
- 230000008929 regeneration Effects 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 26
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 23
- 239000001301 oxygen Substances 0.000 claims description 23
- 229910052760 oxygen Inorganic materials 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 11
- 229910000510 noble metal Inorganic materials 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 claims description 8
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 8
- 230000001172 regenerating effect Effects 0.000 claims description 7
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 238000007664 blowing Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 60
- 229910052757 nitrogen Inorganic materials 0.000 description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 25
- 229910052799 carbon Inorganic materials 0.000 description 25
- 239000002904 solvent Substances 0.000 description 18
- 238000002485 combustion reaction Methods 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 12
- 230000008021 deposition Effects 0.000 description 10
- 239000002923 metal particle Substances 0.000 description 10
- 150000001721 carbon Chemical class 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000010408 sweeping Methods 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides a regeneration method of a molecular sieve catalyst. The regeneration method comprises the following steps: carrying out in-situ treatment on the inactivated molecular sieve catalyst to obtain a treated molecular sieve catalyst, and then carrying out first inert gas purging on the treated molecular sieve catalyst to obtain a first molecular sieve catalyst; by C 6 ～C 15 Washing aromatic hydrocarbon on the surface of the first molecular sieve catalyst to obtain a second molecular sieve catalystA molecular sieve catalyst; purging the second molecular sieve catalyst with a second inert gas to obtain a third molecular sieve catalyst; carrying out first hydrogen blowing on the third molecular sieve catalyst to obtain a fourth molecular sieve catalyst; purging the fourth molecular sieve catalyst with a third inert gas to obtain a fifth molecular sieve catalyst; purging the fifth molecular sieve catalyst by taking inert gas and air as mixed carrier gas to obtain a sixth molecular sieve catalyst; purging the sixth molecular sieve catalyst with a fourth inert gas to obtain a seventh molecular sieve catalyst; a second hydrogen sweep is conducted over the seventh molecular sieve catalyst.
Description
Technical Field
The invention relates to the technical field of catalyst regeneration, in particular to a regeneration method of a molecular sieve catalyst.
Background
The molecular sieve catalyst is widely applied to reaction systems of MTO, MTG, alkane aromatization and the like due to good shape-selective catalytic performance. However, the problem of carbon deposition (or coking) of the catalyst during the reaction process is very common in industrial production, and the catalyst is deactivated due to the coverage of active sites caused by the carbon deposition, thereby limiting the application of the catalyst in industrial manufacturing.
The carbon deposition process of the molecular sieve mainly depends on the acidity and the pore structure of the molecular sieve, and the acidity of the molecular sieve is closely related to the pretreatment temperature, so that the pretreatment temperature is controlled in an optimal range, the coking rate of the catalyst can be reduced or inhibited within a certain range to different degrees, the service life of the catalyst is further effectively prolonged, the use efficiency and the production benefit of the catalyst are brought into full play, and the problem of how to realize the regeneration of the catalyst becomes extremely important and critical.
The regeneration method of the catalyst inactivated by carbon deposition in the traditional molecular sieve catalyst regeneration process mainly comprises carbon burning regeneration and coke dissolving regeneration. During the regeneration of the calcined carbon, the carbon deposition on the surface and pore channels of the catalyst is removed and the catalytic performance is recovered by a method of heating and roasting under a certain carrier gas atmosphere. The regeneration effect is related to factors such as roasting temperature, heating rate, roasting time, carrier gas atmosphere and the like. Under the conditions of too high temperature rise rate, too high roasting temperature, too long roasting time and the like, on one hand, the framework structure of the catalyst can be damaged, the framework is collapsed, even the catalyst is permanently inactivated, on the other hand, the phenomena of 'temperature runaway' and the like of a roasted bed layer can be formed, particularly for a metal-supported molecular sieve catalyst, metal particles are easy to agglomerate, and the performance of the catalyst is further seriously influenced. And if the roasting temperature of the catalyst is too low and the roasting time is too short, the carbon burning is incomplete, and the catalytic performance cannot be effectively recovered.
Disclosure of Invention
The invention mainly aims to provide a regeneration method of a molecular sieve catalyst, which aims to solve the problem that reaction conditions are difficult to control when a charcoal-fired regeneration method is adopted in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for regenerating a molecular sieve catalyst, the molecular sieve catalyst comprising a noble metal-supported molecular sieve catalyst, the method comprising: step S1, carrying out in-situ treatment on the inactivated molecular sieve catalyst to obtain a treated molecular sieve catalyst, and then carrying out first inert gas purging on the treated molecular sieve catalyst to obtain a first molecular sieve catalyst; step S2, using C 6 ～C 15 Washing aromatic hydrocarbon substances on the surface of the first molecular sieve catalyst to obtain a second molecular sieve catalyst; s3, carrying out second inert gas purging on the second molecular sieve catalyst to obtain a third molecular sieve catalystA molecular sieve catalyst; s4, performing first hydrogen sweeping on the third molecular sieve catalyst to obtain a fourth molecular sieve catalyst; s5, carrying out third inert gas purging on the fourth molecular sieve catalyst to obtain a fifth molecular sieve catalyst; s6, purging the fifth molecular sieve catalyst by taking inert gas and air as mixed carrier gas to obtain a sixth molecular sieve catalyst; s7, carrying out fourth inert gas purging on the sixth molecular sieve catalyst to obtain a seventh molecular sieve catalyst; and S8, carrying out second hydrogen purge on the seventh molecular sieve catalyst to obtain a regenerated molecular sieve catalyst.
Further, the step of in situ processing comprises: filling the inactivated molecular sieve catalyst into a fixed bed reactor, heating the fixed bed reactor to 80-150 ℃ for in-situ treatment, preferably, the heating rate of the in-situ treatment is 2-5 ℃/min, and the treatment time is 24-48 h.
Further, the volume space velocity of the first inert gas purging is 180-220 h -1 The time of the first inert gas purging is preferably 1 to 3 hours, and the pressure of the first inert gas purging is preferably 101kPa.
Further, C 6 ～C 15 The aromatic hydrocarbon is selected from one or more of toluene, ethylbenzene, diethylbenzene, dimethylbenzene, isopropylbenzene, pseudocumene and mesitylene; preferably, C 6 ～C 15 The flow rate of the aromatic hydrocarbon is 1 to 4 hours -1 Preferably C 6 ～C 15 The time for introducing the aromatic hydrocarbon into the fixed bed reactor is 12-24 hours.
Further, the volume space velocity of the second inert gas purging is 200-500 h -1 Preferably, the time for purging the second inert gas is 10-20 h, and the pressure for purging the second inert gas is 101kPa; preferably, the reaction temperature of the second inert gas purging is 150-300 ℃, the heating rate of heating to the reaction temperature is 2-5 ℃/min, and the treatment time is 24-48 h.
Further, the temperature of the first hydrogen purging reaction is 200-250 ℃, the pressure of the first hydrogen purging is preferably 0-2 MPa, and the volume space velocity of the first hydrogen purging is preferably 200-500 h -1 Preferably firstThe time of hydrogen purging is 12-24 h.
Further, the temperature of the third inert gas purging reaction is 400-600 ℃, the time of the third inert gas purging is preferably 1-3 h, and the pressure of the third inert gas purging is preferably 101kPa.
Further, in step S6, the volume space velocity of the mixed carrier gas is 200-500 h -1 The mass content of oxygen in the mixed carrier gas is preferably 1 to 5%, and the purge time is preferably 40 to 60 hours.
Further, the pressure of the fourth inert gas purging is 101kPa, and the time of the fourth inert gas purging reaction is preferably 1-3 h; preferably, the temperature of the second hydrogen purging is 250-350 ℃, the pressure of the second hydrogen purging is 0-2 MPa, and the volume space velocity of the second hydrogen purging is 200-500 h -1 。
Further, the deactivated molecular sieve catalyst comprises a deactivated catalyst obtained in a Fischer-Tropsch wax hydroisomerization reaction stage; preferably, the noble metal in the molecular sieve catalyst is Pt and/or Pd, more preferably, the molecular sieve catalyst is one or more selected from Pt/ZSM-48, pt/ZSM-22 and Pt/ZSM-23, and even more preferably, the molecular sieve catalyst is Pt/ZSM-48 molecular sieve catalyst.
By applying the technical scheme of the invention, firstly, in-situ treatment and first inert gas purging are utilized to remove impurities such as oil wax on the surface of the molecular sieve catalyst and replace oxygen in a reaction system, so that oxygen is prevented from participating in a combustion reaction; then using C 6 ～C 15 The aromatic hydrocarbon is used as a solvent to remove aromatic hydrocarbon substances on the surface of the molecular sieve catalyst; the unsaturated carbon-containing substances on the metal surface can be saturated by adopting hydrogen treatment, so that the unsaturated carbon-containing substances can be removed more easily; and then purging by using inert gas to remove small molecular impurities, and finally burning the carbon in an oxygen-poor combustion mode, wherein part of carbon deposition of heavy aromatics is removed, and then the oxygen-poor combustion mode is adopted to effectively reduce the temperature runaway of a catalyst bed layer, so that the high dispersion of noble metal particles in the molecular sieve catalyst is effectively ensured, and the catalytic performance of the regenerated catalyst is ensured. The regeneration method is simple to operate, has no excessive requirements on reaction conditions, and can effectively reduce energy consumption and pollution; at the same timeThe method adopts an in-device regeneration mode, does not need to disassemble the catalyst, does not need to prepare the catalyst, and has lower regeneration cost.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As analyzed by the background technology of the application, in the traditional charcoal-fired regeneration process, under the conditions of too high temperature rise rate, too high roasting temperature, too long roasting time and the like, on one hand, the framework structure of the catalyst can be damaged, so that the framework is collapsed, even the catalyst is permanently inactivated, on the other hand, the phenomena of 'temperature runaway' of a roasting bed layer and the like can be caused, and particularly for a metal-loaded molecular sieve catalyst, metal particles are easy to agglomerate, so that the performance of the catalyst is seriously influenced. And if the roasting temperature of the catalyst is too low and the roasting time is too short, the carbon burning is incomplete, and the catalytic performance cannot be effectively recovered. In order to solve the above problems, the present application provides a method for regenerating a molecular sieve catalyst.
In one exemplary embodiment, a method for regenerating a molecular sieve catalyst comprising a noble metal-supported molecular sieve catalyst is provided, the method comprising: step S1, carrying out in-situ treatment on the deactivated molecular sieve catalyst to obtain a treated molecular sieve catalyst, and then carrying out first inert gas purging on the treated molecular sieve catalyst to obtain a first molecular sieve catalyst; step S2, using C 6 ～C 15 Washing aromatic hydrocarbon substances on the surface of the first molecular sieve catalyst to obtain a second molecular sieve catalyst; s3, carrying out second inert gas purging on the second molecular sieve based catalyst to obtain a third molecular sieve based catalyst; s4, performing first hydrogen sweeping on the third molecular sieve catalyst to obtain a fourth molecular sieve catalyst; s5, carrying out third inert gas purging on the fourth molecular sieve catalyst to obtain a fifth molecular sieve catalyst; s6, purging the fifth molecular sieve catalyst by taking inert gas and air as mixed carrier gas to obtain a sixth molecular sieve catalyst; step S7, the sixth molecular sieve catalystPurging with a fourth inert gas to obtain a seventh molecular sieve catalyst; and S8, carrying out second hydrogen purge on the seventh molecular sieve catalyst to obtain a regenerated molecular sieve catalyst.
The inventor researches to find that when the molecular sieve catalyst is applied to the hydroisomerization reaction of Fischer-Tropsch wax, the main reasons of the deactivation are as follows: firstly, the by-product is deposited on the surface of the catalyst to cover the active site, thereby seriously affecting the catalytic performance; secondly, various metal organic compounds contained in the Fischer-Tropsch wax serving as a reaction raw material are deposited on the surface of the catalyst, so that the catalyst is deactivated. Aiming at the inactivation reason of the molecular sieve catalyst in a hydroisomerization reaction system, the method of stepwise and sectional decarburization is adopted, carbon deposition substances on the surface of the catalyst and metal compounds possibly existing are effectively removed, meanwhile, the dispersion degree of noble metals loaded on the molecular sieve is not changed, the industrial regeneration of the inactivated molecular sieve catalyst is realized, and the performance of the regenerated catalyst reaches the level of a fresh catalyst.
The method comprises the steps of replacing by inert gas, dissolving out part of carbon deposit by adopting a proper organic solvent, purging residual solvent and part of carbon deposit on the surface of the catalyst by using inert gas, and saturating part of unsaturated carbon deposit by adopting hydrogen. In order to ensure safety, inert gas is used for replacement, and then oxygen-deficient air is used for burning off residual carbon deposition substances. Specifically, the method comprises the steps of firstly removing impurities such as oil wax on the surface of a molecular sieve catalyst and replacing oxygen in a reaction system by in-situ treatment and first inert gas purging to avoid oxygen participating in a combustion reaction; then using C 6 ～C 15 The aromatic hydrocarbon is used as a solvent to remove aromatic hydrocarbon substances on the surface of the molecular sieve catalyst; the unsaturated carbon-containing substances on the metal surface can be saturated by adopting hydrogen treatment, so that the unsaturated carbon-containing substances can be removed more easily; and then purging by using inert gas to remove small molecular impurities, and finally burning the carbon in an oxygen-poor combustion mode, wherein part of carbon deposition of heavy aromatics is removed, and then the oxygen-poor combustion mode is adopted to effectively reduce the temperature runaway of a catalyst bed layer, so that the high dispersion of noble metal particles in the molecular sieve catalyst is effectively ensured, and the catalytic performance of the regenerated catalyst is ensured. Regeneration of the present applicationThe method is simple to operate, has no excessive requirements on reaction conditions, and can effectively reduce energy consumption and pollution; meanwhile, the in-reactor regeneration mode is adopted, the catalyst does not need to be disassembled, the standby catalyst does not need to be used, and the regeneration cost is low.
In order to remove impurities such as oil wax adhering to the deactivated molecular sieve catalyst, in some embodiments, the in situ treatment step comprises: filling the deactivated molecular sieve catalyst into a fixed bed reactor, heating the fixed bed reactor to 80-150 ℃ for in-situ treatment, preferably, the heating rate of the in-situ treatment is 2-5 ℃/min, and the treatment time is 24-48 h. Too high temperature or too fast temperature increase rate of in-situ treatment easily causes agglomeration of the metal particles supported on the catalyst, and the process of metal particle agglomeration is irreversible, thereby affecting the activity of the catalyst. The temperature and the temperature rise rate of the in-situ treatment are in the ranges, and the relatively high temperature and the relatively low temperature are selected, so that the regeneration effect of the catalyst is improved.
In order to more completely displace the oxygen in the reaction system, in some embodiments, the first inert gas purge has a volumetric space velocity of 180 to 220 hours -1 The time for purging the first inert gas is 1-3 h.
The kind of the inert gas is not particularly limited, and helium, nitrogen, argon may be applied to the present application. In view of economic cost, nitrogen is preferred.
In order to achieve sufficient solubility of the aromatic species on the deactivated molecular sieve catalyst for purposes of removing the aromatic species, in some embodiments, C 6 ～C 15 The aromatic hydrocarbon is selected from one or more of toluene, ethylbenzene, diethylbenzene, dimethylbenzene, isopropylbenzene, pseudocumene and mesitylene; since aromatic hydrocarbon substance has better solubility in cumene, the above C 6 ～C 15 The aromatic hydrocarbon of (a) is preferably cumene. Preferably, C 6 ～C 15 The flow rate of the aromatic hydrocarbon is 1 to 4 hours -1 Preferably C 6 ～C 15 The time for introducing the aromatic hydrocarbon into the fixed bed reactor is 12-24 hours. In the utilization of C 6 ～C 15 When the aromatic hydrocarbon is used as a solvent to wash off aromatic hydrocarbon substances on the surface of the molecular sieveThe solvent can be recovered and recycled.
In order to remove residual solvent and part of carbon deposit on the surface of the catalyst, in some embodiments, the volume space velocity of the second inert gas purging is 200-500 h -1 Preferably, the time for purging the second inert gas is 10-20 h, and the pressure for purging the second inert gas is 101kPa; reaction temperature of the second inert gas purge and C 6 ～C 15 The boiling point of the aromatic hydrocarbon solvent is related, and the temperature cannot be too low, which would result in poor catalytic performance of the regenerated catalyst.
In order to sufficiently remove the solvent, the reaction temperature of the second inert gas purge is preferably 150 to 300 ℃, the heating rate of heating to the reaction temperature is preferably 2 to 5 ℃/min, and the time of the second inert gas purge is 24 to 48 hours.
Because the Fischer-Tropsch wax hydroisomerization reaction can leave unsaturated hydrocarbon substances on the surface of the catalyst, and C = C in the unsaturated hydrocarbon substances has a strong adsorption effect on the catalyst, the unsaturated hydrocarbon substances and hydrogen are hydrogenated to form saturated hydrocarbon substances, and the saturated hydrocarbon substances can be easily removed from the surface of the molecular sieve catalyst. In some embodiments, the temperature of the first hydrogen purge is 200 to 250 ℃, preferably the pressure of the first hydrogen purge is 0 to 2MPa, and increasing the pressure appropriately facilitates catalyst regeneration. The volume space velocity of the first hydrogen purge is preferably 200 to 500h -1 Preferably, the time of the first hydrogen purge is 12 to 24 hours. Too high a temperature of the first hydrogen purge may affect the dispersion of the metal particles. It should be noted that the pressure herein refers to gauge pressure.
In order to further remove small molecular substances on the surface of the molecular sieve catalyst and replace hydrogen, and avoid damaging the framework structure of the catalyst due to overhigh temperature. In some embodiments, the temperature of the third inert gas purge is 400 to 600 ℃, preferably the time of the third inert gas purge reaction is 1 to 3 hours, and preferably the pressure of the third inert gas purge reaction is 101kPa. And because the temperature of the subsequent oxygen-poor combustion is relatively high, in order to reach the combustion temperature as soon as possible and be beneficial to catalyst regeneration, the temperature of the third inert gas purging is slightly higher than the temperature of the first inert gas purging and the second inert gas purging.
In the prior art, the method for regenerating the calcined carbon directly roasts the catalyst at high temperature, but because the carbon content in the catalyst is higher and the roasting temperature is relatively higher, the agglomeration of noble metal particles is easily caused, and the catalytic performance of the catalyst is further influenced. According to the method, the catalyst is decarbonized and then roasted in the oxygen-poor atmosphere, so that the surface temperature of the catalyst is low, the reaction heat is low, the noble metal particles are not easy to agglomerate, and the energy consumption can be effectively reduced. In some embodiments, the volume space velocity of the mixed carrier gas in step S6 is 200-500 h -1 The mass content of oxygen in the mixed carrier gas is preferably 1-5%, compared with the prior art, the oxygen content is reduced, carbon on the surface of the catalyst is gradually burnt, and the influence of strong heat release on the performance of the catalyst is avoided. The preferred time for purging is 40 to 60 hours. If the mass content of oxygen in the mixed carrier gas is too high, the catalytic performance of the catalyst can be influenced due to strong heat release in the combustion process, and if the mass content of oxygen in the mixed carrier gas is too low, incomplete carbon burning can be caused, and the catalytic performance of the catalyst cannot be effectively recovered.
In some embodiments, the pressure of the fourth inert gas purge is 101kPa, preferably the time of the fourth inert gas purge is 1 to 3 hours; preferably, the temperature of the second hydrogen purging is 250-350 ℃, the pressure of the second hydrogen purging is 0-2 MPa, and the volume space velocity of the second hydrogen purging is 200-500 h -1 . After the molecular sieve catalyst is subjected to oxygen-deficient combustion, the fourth inert gas is used for purging and removing small molecular substances generated by combustion, oxygen in the system is replaced, and then hydrogen is used for reduction reaction.
There is no particular limitation on the type of molecular sieve catalyst used herein, and any molecular sieve catalyst of a Fischer-Tropsch wax hydroisomerization production lubricating oil system may be used herein. In some embodiments, the molecular sieve catalyst comprises a deactivated catalyst obtained from a fischer-tropsch wax hydroisomerization reaction stage; preferably, the noble metal in the molecular sieve catalyst is Pt and/or Pd, the molecular sieve catalyst is selected from one or more of Pt/ZSM-48, pt/ZSM-22 and Pt/ZSM-23, and the molecular sieve catalyst is Pt/ZSM-48 molecular sieve catalyst.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
(1) Filling the inactivated molecular sieve catalyst Pt/ZSM-48 in a fixed bed reactor, and heating the reactor to 120 ℃ for in-situ treatment at the heating rate of 2 ℃/min for 25h to obtain the treated molecular sieve catalyst;
(2) Firstly, nitrogen is introduced into a reactor, and the volume space velocity is 200h -1 Carrying out first nitrogen purging for 2h at normal pressure to replace oxygen in the reaction system, and then closing the gas circuit to obtain a first molecular sieve catalyst;
(3) Cumene was used as solvent, and the flow rate was controlled at 3h -1 Introducing cumene into a fixed bed reactor for 15 hours, washing off aromatic substances on the surface of the first molecular sieve catalyst, and recycling the solvent to obtain a second molecular sieve catalyst;
(4) After the step (3) is finished, the solvent feeding pipeline is closed, nitrogen gas is introduced to carry out secondary nitrogen purging, purging is carried out for 12 hours under normal pressure, and the space velocity of the carrier gas volume is 400 hours -1 . Simultaneously heating the reactor to 240 ℃ at the heating rate of 2 ℃/min to obtain a third molecular sieve catalyst;
(5) And closing the inert gas path, and replacing the carrier gas with hydrogen. Introducing hydrogen into a reactor for first hydrogen sweeping, keeping the temperature of the reactor unchanged, adjusting the pressure to 0.5MPa, and adjusting the space velocity of the carrier gas volume to 400h -1 Keeping the temperature for 12 hours;
(6) And closing a hydrogen gas path, replacing the carrier gas with nitrogen, performing third nitrogen purging for 2 hours under normal pressure to replace the hydrogen in the reaction system, and simultaneously heating the temperature of the reactor to 450 ℃ to obtain the fourth molecular sieve catalyst.
(7) Introducing a proper amount of air into the reactor for blowing reaction, controlling the oxygen content to be 1.5% by controlling the nitrogen flow, and controlling the volume space velocity of the carrier gas to be 400h -1 The reaction is maintained for 50h under the conditions, and the deactivated catalyst is regenerated.
(8) Then the carrier gas is replaced by nitrogen gas, inAnd (5) closing the nitrogen gas path after carrying out fourth nitrogen purging for 2 hours at normal pressure. Introducing hydrogen into the fixed bed reactor, and performing second hydrogen purging with the pressure of 0.5MPa and the volume space velocity of 400h -1 And the temperature of the second hydrogen purging is 250 ℃, and after the catalyst is reduced, the catalyst regeneration is completed.
Example 2
(1) Filling the inactivated molecular sieve catalyst Pt/ZSM-48 in a fixed bed reactor, heating the reactor to 150 ℃, and obtaining the treated molecular sieve catalyst, wherein the heating rate is 5 ℃/min;
(2) Firstly, nitrogen is introduced into a reactor, and the volume space velocity is 220h -1 Carrying out first nitrogen purging for 3h at normal pressure to replace oxygen in the reaction system, and then closing the gas circuit to obtain a first molecular sieve catalyst;
(3) Cumene was used as solvent, and the flow rate was controlled at 4h -1 Introducing cumene into a fixed bed reactor for 12 hours, washing off aromatic substances on the surface of the first molecular sieve catalyst, and recycling the solvent to obtain a second molecular sieve catalyst;
(4) After the step (3) is finished, the solvent feeding pipeline is closed, nitrogen is introduced to carry out secondary nitrogen purging, the purging is carried out for 20 hours under normal pressure, and the space velocity of the carrier gas volume is 500 hours -1 . Simultaneously heating the reactor to 250 ℃ at the heating rate of 5 ℃/min to obtain a third molecular sieve catalyst;
(5) And closing the nitrogen gas path, and replacing the carrier gas with hydrogen. Introducing hydrogen into a reactor for first hydrogen sweeping, keeping the temperature of the reactor unchanged, adjusting the pressure to be 2MPa, and adjusting the volume space velocity of carrier gas to be 500h -1 Keeping the temperature for 24 hours under the condition;
(6) And closing a hydrogen gas path, replacing the carrier gas with nitrogen, performing third nitrogen purging for 2 hours at normal pressure to replace the hydrogen in the reaction system, and simultaneously heating the temperature of the reactor to 600 ℃ to obtain the fourth molecular sieve catalyst.
(7) Introducing a proper amount of air into the reactor for purging, controlling the oxygen content at 5% by controlling the nitrogen flow, and controlling the volume space velocity of the carrier gas at 500h -1 Conditions of this kindKeeping for 40h, and regenerating the deactivated catalyst.
(8) And then changing the carrier gas into nitrogen, performing fourth nitrogen purging for 3 hours at normal pressure, and closing the nitrogen gas path. Introducing hydrogen into the fixed bed reactor, and performing second hydrogen purging at a pressure of 2MPa and a volume space velocity of 500h -1 And the temperature of the second hydrogen purging is 350 ℃, and after the catalyst is reduced, the catalyst regeneration is completed.
Example 3
(1) Filling the inactivated molecular sieve catalyst Pt/ZSM-48 in a fixed bed reactor, heating the reactor to 80 ℃, wherein the heating rate is 3 ℃/min, and obtaining the treated molecular sieve catalyst;
(2) Firstly, nitrogen is introduced into a reactor, and the volume space velocity is 180h -1 Carrying out first nitrogen purging for 1 hour at normal pressure to replace oxygen in the reaction system, and then closing the gas circuit to obtain a first molecular sieve catalyst;
(3) Cumene was used as solvent, and the flow rate was controlled at 1h -1 Introducing cumene into a fixed bed reactor for 24 hours, washing off aromatic hydrocarbon substances on the surface of the first molecular sieve catalyst, and recycling the solvent to obtain a second molecular sieve catalyst;
(4) After the step (3) is finished, the solvent feeding pipeline is closed, nitrogen is introduced to carry out secondary nitrogen purging, purging is carried out for 10 hours under normal pressure, and the space velocity of the carrier gas volume is 200 hours -1 . Simultaneously heating the reactor to 200 ℃ at the heating rate of 2 ℃/min to obtain a third molecular sieve catalyst;
(5) And closing the nitrogen gas path, and replacing the carrier gas with hydrogen. Introducing hydrogen into the reactor to perform first hydrogen purging, keeping the temperature of the reactor unchanged, adjusting the pressure of a pressure gauge to be 0MPa, and adjusting the volume airspeed of carrier gas to be 200h -1 Keeping the temperature for 24 hours under the condition;
(6) And closing a hydrogen gas path, replacing the carrier gas with nitrogen, performing third nitrogen purging for 2 hours at normal pressure to replace the hydrogen in the reaction system, and simultaneously heating the temperature of the reactor to 400 ℃ to obtain the fourth molecular sieve catalyst.
(7) Introducing a proper amount of water into the reactorThe oxygen content is controlled to be 1 percent by controlling the nitrogen flow, and the space velocity of the carrier gas volume is 200h -1 And keeping the temperature for 60 hours under the condition, and regenerating the deactivated catalyst with the carbon deposition mass fraction of 10%.
(8) And then changing the carrier gas into nitrogen, performing fourth nitrogen purging for 1 hour under normal pressure, and closing the nitrogen gas circuit. Introducing hydrogen into the fixed bed reactor, and performing second hydrogen purging at a pressure of 0MPa and a volume space velocity of 200h -1 And the temperature of the second hydrogen purging is 300 ℃, and after the catalyst is reduced, the catalyst regeneration is completed.
Example 4
Unlike example 1, in step (7), the oxygen content was 6%.
Example 5
Unlike example 1, in step (5), the pressure of the first hydrogen purge was 2.5MPa.
Example 6
Unlike example 1, the deactivated molecular sieve catalyst was Pt/ZSM-22.
Example 7
Unlike example 1, in step (3), pseudocumene was used as a solvent.
Example 8
In contrast to example 1, ethylbenzene was used as a solvent in step (3).
Example 9
Unlike example 1, in step (1), the temperature increase rate of the in-situ treatment was 6 ℃/min.
Example 10
Unlike example 1, the temperature of the in situ treatment in step (1) was 160 ℃.
Example 11
Unlike example 1, in step (4), the time for the second nitrogen purge was 8 hours.
Example 12
Unlike example 1, in step (3), cumene was passed through for 10 hours.
The activity ratio of the re-hydroisomerization reaction of the regenerated catalyst and the fresh catalyst of each example and comparative example is shown in table 1.
TABLE 1
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: firstly, removing impurities such as oil wax on the surface of a molecular sieve catalyst and replacing oxygen in a reaction system by utilizing in-situ treatment and first inert gas purging reaction to avoid oxygen participating in combustion reaction; then, heavy aromatic hydrocarbon is used as a solvent to remove aromatic hydrocarbon substances on the surface of the molecular sieve catalyst; then, the unsaturated carbon-containing substances on the metal surface can be saturated by adopting hydrogen treatment, so that the unsaturated carbon-containing substances can be removed more easily; and then, removing small molecular impurities by using inert gas purging reaction, and finally burning carbon by adopting an oxygen-poor combustion mode, wherein part of carbon deposition of heavy aromatics is removed, and then, the oxygen-poor combustion mode can effectively reduce the temperature runaway of a catalyst bed layer, so that the high dispersion of noble metal particles in the molecular sieve catalyst is effectively ensured, and the catalytic performance of the regenerated catalyst is ensured. The regeneration method is simple to operate, has no excessive requirements on reaction conditions, and can effectively reduce energy consumption and pollution; meanwhile, the in-reactor regeneration mode is adopted, the catalyst does not need to be disassembled, the standby catalyst does not need to be used, and the regeneration cost is low.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method of regenerating a molecular sieve catalyst, the molecular sieve catalyst comprising a noble metal-loaded molecular sieve catalyst, the method comprising:
step S1, carrying out in-situ treatment on the deactivated molecular sieve catalyst to obtain a treated molecular sieve catalyst, and then carrying out first inert gas purging on the treated molecular sieve catalyst to obtain a first molecular sieve catalyst;
step S2, using C 6 ～C 15 Washing aromatic hydrocarbon substances on the surface of the first molecular sieve catalyst to obtain a second molecular sieve catalyst;
s3, carrying out second inert gas purging on the second molecular sieve catalyst to obtain a third molecular sieve catalyst;
s4, performing first hydrogen gas purging on the third molecular sieve based catalyst to obtain a fourth molecular sieve based catalyst;
s5, carrying out third inert gas purging on the fourth molecular sieve catalyst to obtain a fifth molecular sieve catalyst;
s6, purging the fifth molecular sieve catalyst by taking inert gas and air as mixed carrier gas to obtain a sixth molecular sieve catalyst;
s7, performing fourth inert gas purging on the sixth molecular sieve catalyst to obtain a seventh molecular sieve catalyst;
and S8, carrying out second hydrogen purge on the seventh molecular sieve catalyst to obtain a regenerated molecular sieve catalyst.
2. The regeneration method according to claim 1, wherein the step of in situ treating comprises: and filling the inactivated molecular sieve catalyst into a fixed bed reactor, and heating the fixed bed reactor to 80-150 ℃ for in-situ treatment, wherein the heating rate of the in-situ treatment is preferably 2-5 ℃/min, and the treatment time is 24-48 h.
3. Regeneration process according to claim 1 or 2, characterized in that the first inert gas purge has a volumetric space velocity of between 180 and 220h -1 Preferably, the time of the first inert gas purging is 1 to 3 hours, and the pressure of the first inert gas purging is 101kPa.
4. Regeneration process according to any one of claims 1 to 3, characterized in that C is the product of the reaction 6 ～C 15 The aromatic hydrocarbon is selected from one or more of toluene, ethylbenzene, diethylbenzene, dimethylbenzene, isopropylbenzene, pseudocumene and mesitylene;
preferably, said C 6 ～C 15 The flow rate of the aromatic hydrocarbon is 1 to 4 hours -1 Preferably said C 6 ～C 15 The time for introducing the aromatic hydrocarbon into the fixed bed reactor is 12-24 hours.
5. Regeneration process according to any one of claims 1 to 3, characterized in that the second inert gas purge has a volumetric space velocity of between 200 and 500h -1 Preferably, the time for purging the second inert gas is 10-20 h, and the pressure for purging the second inert gas is 101kPa;
preferably, the reaction temperature of the second inert gas purging is 150-300 ℃, the heating rate of heating to the reaction temperature is 2-5 ℃/min, and the treatment time is 24-48 h.
6. Regeneration process according to any one of claims 1 to 3, characterized in that the temperature of the first hydrogen sweep reaction is between 200 and 250 ℃, preferably the pressure of the first hydrogen sweep is between 0 and 2MPa, preferably the volumetric space velocity of the first hydrogen sweep is between 200 and 500h -1 Preferably, the time of the first hydrogen purge is 12 to 24 hours.
7. Regeneration process according to any one of claims 1 to 3, characterized in that the temperature of the third inert gas purge reaction is 400-600 ℃, preferably the time of the third inert gas purge is 1-3 h, preferably the pressure of the third inert gas purge is 101kPa.
8. Root of herbaceous plantThe regeneration process according to any one of claims 1 to 3, wherein the volume space velocity of the mixed carrier gas in step S6 is 200 to 500h -1 The mass content of oxygen in the mixed carrier gas is preferably 1 to 5%, and the purging time is preferably 40 to 60 hours.
9. Regeneration process according to any one of claims 1 to 3, characterized in that the pressure of the fourth inert gas purge is 101kPa, preferably the time of the fourth inert gas purge reaction is between 1 and 3h;
preferably, the temperature of the second hydrogen purging is 250-350 ℃, the pressure of the second hydrogen purging is 0-2 MPa, and the volume space velocity of the second hydrogen purging is 200-500 h -1 。
10. The regeneration process of any one of claims 1 to 9, wherein the deactivated molecular sieve catalyst comprises a deactivated catalyst obtained from a fischer-tropsch wax hydroisomerization reaction stage; preferably, the noble metal in the molecular sieve catalyst is Pt and/or Pd, more preferably, the molecular sieve catalyst is one or more selected from Pt/ZSM-48, pt/ZSM-22 and Pt/ZSM-23, and even more preferably, the molecular sieve catalyst is Pt/ZSM-48 molecular sieve catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211428228.1A CN115845933A (en) | 2022-11-15 | 2022-11-15 | Regeneration method of molecular sieve catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211428228.1A CN115845933A (en) | 2022-11-15 | 2022-11-15 | Regeneration method of molecular sieve catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115845933A true CN115845933A (en) | 2023-03-28 |
Family
ID=85663532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211428228.1A Pending CN115845933A (en) | 2022-11-15 | 2022-11-15 | Regeneration method of molecular sieve catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115845933A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050187095A1 (en) * | 2004-02-24 | 2005-08-25 | Grey Roger A. | Catalyst regeneration process |
| CA2574347A1 (en) * | 2006-01-25 | 2007-07-25 | Air Products And Chemicals, Inc. | Hydrogen production process with regenerant recycle |
| US20100099549A1 (en) * | 2008-10-22 | 2010-04-22 | Myers Daniel N | Once Through Regeneration for an Olefin Cracking Reactor |
| CN102847545A (en) * | 2012-09-29 | 2013-01-02 | 中国天辰工程有限公司 | Regeneration method of ruthenium-zinc catalyst for partial hydrogenation of benzene |
| CN104107703A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Regeneration method of olefin disproportionation reaction catalyst |
| CN110075866A (en) * | 2016-09-22 | 2019-08-02 | 福建省福大百阳化工科技有限公司 | A kind of palladium catalyst regeneration method of high activity |
| CN111203287A (en) * | 2018-11-21 | 2020-05-29 | 内蒙古伊泰煤基新材料研究院有限公司 | Regeneration method of benzene alkylation solid acid catalyst |
| CN111330630A (en) * | 2020-03-18 | 2020-06-26 | 国家能源集团宁夏煤业有限责任公司 | Molecular sieve catalyst, preparation method thereof and liquefied petroleum gas alkylation reaction method |
-
2022
- 2022-11-15 CN CN202211428228.1A patent/CN115845933A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050187095A1 (en) * | 2004-02-24 | 2005-08-25 | Grey Roger A. | Catalyst regeneration process |
| CA2574347A1 (en) * | 2006-01-25 | 2007-07-25 | Air Products And Chemicals, Inc. | Hydrogen production process with regenerant recycle |
| US20100099549A1 (en) * | 2008-10-22 | 2010-04-22 | Myers Daniel N | Once Through Regeneration for an Olefin Cracking Reactor |
| CN102847545A (en) * | 2012-09-29 | 2013-01-02 | 中国天辰工程有限公司 | Regeneration method of ruthenium-zinc catalyst for partial hydrogenation of benzene |
| CN104107703A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Regeneration method of olefin disproportionation reaction catalyst |
| CN110075866A (en) * | 2016-09-22 | 2019-08-02 | 福建省福大百阳化工科技有限公司 | A kind of palladium catalyst regeneration method of high activity |
| CN111203287A (en) * | 2018-11-21 | 2020-05-29 | 内蒙古伊泰煤基新材料研究院有限公司 | Regeneration method of benzene alkylation solid acid catalyst |
| CN111330630A (en) * | 2020-03-18 | 2020-06-26 | 国家能源集团宁夏煤业有限责任公司 | Molecular sieve catalyst, preparation method thereof and liquefied petroleum gas alkylation reaction method |
Non-Patent Citations (2)
| Title |
|---|
| FÜRCHT, A ET.AL: "n-octane reforming over modified catalysts:: Effect of regeneration on the catalyst performance", 《REACTION KINETICS AND CATALYSIS LETTERS 》, 1 January 2002 (2002-01-01), pages 227 - 233 * |
| 张晓静;刘雁;陈永生;: "负载型ZSM-5分子筛催化剂再生方法研究", 工业催化, no. 06, 15 June 2008 (2008-06-15), pages 28 - 31 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107866285B (en) | Regeneration method of isodewaxing catalyst | |
| CN113453797A (en) | Catalyst structure and process for upgrading hydrocarbons in the presence of a catalyst structure | |
| CN102051205A (en) | In-situ presulfurization method of hydrogenation catalyst | |
| CN109692706B (en) | Regeneration method of molecular sieve catalyst | |
| CN101327441A (en) | Cobalt-based catalyst for selectively synthesizing middle distillate from synthesis gas and production method and use | |
| CN102311766A (en) | Class II active center hydrogenation catalyst start-up vulcanization method | |
| CN108311176B (en) | In-situ activation method of catalyst | |
| CN114130313B (en) | C is to be 3 -C 9 Fluidized bed continuous reaction regeneration system and method for converting alkane into aromatic hydrocarbon | |
| CN115845933A (en) | Regeneration method of molecular sieve catalyst | |
| CN111530493B (en) | Catalyst for converting alkane into aromatic hydrocarbon, preparation method and use method | |
| JP2012530805A (en) | Boiling bed method for processing biocomponent feedstocks | |
| CN101445746B (en) | Pre-passivation method for continuous reforming device | |
| CN110935473B (en) | Hydrodeoxygenation catalyst and preparation method and application thereof | |
| CN102744078B (en) | Hydrogenation catalyst for sulfur-containing liquefied gas at low temperature, and preparation method and application thereof | |
| CN101260319B (en) | Vulcanization method for hydrogenation catalyst | |
| CN104549558A (en) | Reducing method of semi-regenerative reforming catalyst | |
| WO2012074613A1 (en) | Method of regenerating zeolite catalyst | |
| CN106179492B (en) | The revivifier and rejuvenation method and purposes of MTP decaying catalyst | |
| CN107987878B (en) | Method for producing high-octane gasoline | |
| CN111378502B (en) | Method for producing aromatic hydrocarbon solvent oil by hydrogenating C9 aromatic hydrocarbon fraction cracked by ethylene | |
| CN104447172B (en) | The renovation process of oxygen-free dehydrogenating aromatization of methane catalyst | |
| CN102580765A (en) | Reproduction method of coal tar hydrofining catalyst | |
| CN109395731B (en) | Polycyclic aromatic hydrocarbon selective hydrogenation catalyst | |
| CN113522314A (en) | Regeneration method of carbon deposit inactivation hydrogenation catalyst | |
| CN113000074B (en) | Regeneration method of hydrogenation catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |