CN102371189B - Reactivation method for Fishcer-Tropshc synthesis catalyst - Google Patents
Reactivation method for Fishcer-Tropshc synthesis catalyst Download PDFInfo
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Abstract
The invention provides a reactivation method for a Fishcer-Tropshc synthesis catalyst. According to the invention, a Fishcer-Tropshc synthesis catalyst to be activated contacts with inert gas containing a small amount of hydrogen under a mild condition at first and then contacts with pure hydrogen at high temperature. Application of the method provided in the invention for activation treatment of a fixed bed Fishcer-Tropshc synthesis catalyst enables the phenomenon of excess temperature to be avoided and the performance of the activated fixed bed Fishcer-Tropshc synthesis catalyst to recover well.
Description
Technical field
The present invention relates to a kind of process for reactivation of catalyst, more particularly, relate to a kind of process for reactivation of fixed bed FischerTropsch synthesis catalyst.
Background technology
The synthetic advantage simple to operate due to it, that the heavy hydrocarbon yield is high of fixed bed Fischer-Tropsch is used as one of major technique of the synthetic exploitation of Fischer-Tropsch.In the device running, along with the fischer-tropsch synthetic catalyst prolongation of the duration of runs, fischer-tropsch synthetic catalyst is active, selectively all can decrease, and after to a certain degree, need to process to improve catalyst performance when the fischer-tropsch synthetic catalyst activity decreased to fischer-tropsch synthetic catalyst.The processing method of recovering the fischer-tropsch synthetic catalyst performance comprises two kinds of reactivation of catalyst and catalyst regenerations.In general, comprise a plurality of activation process steps in the regeneration period of fischer-tropsch synthetic catalyst, and effectively the activation method of fischer-tropsch synthetic catalyst is one of key technology of fischer-tropsch synthetic catalyst long-term operation.
US6022755 discloses a kind of activation method of fischer-tropsch synthetic catalyst, and the method is under Fischer-Tropsch synthetic operation pattern, reduces gradually the content of CO in unstripped gas, to reactor outlet H
2/ CO the regular hour of turning round under this operating mode, makes catalyst performance obtain part and recovers than surpassing 10: 1.
US6486220 discloses a kind of activation method of fischer-tropsch synthetic catalyst, and the method is that reclaimable catalyst carries out activation process in containing the atmosphere of steam.The activation process condition is: 250～350 ℃ of temperature, soak time 4h, activated gas volume space velocity at least 0.5, activation pressure 10～350pisg, activated gas at least contain the hydrogen that is no more than 10 volume %.
US2003166451 discloses a kind of renovation process of fischer-tropsch synthetic catalyst, and the method is taked in interior hydrogen atmosphere, catalyst to be processed including ammonia or weak organic acid, and the catalyst performance after processing obtains part and recovers.
But, in fischer-tropsch synthetic catalyst activation process, regulated not at that time when reaction atmosphere and operating temperature, serious overheating problem can occur, and overtemperature can damage the activity of fischer-tropsch synthetic catalyst, finally cause the fischer-tropsch synthetic catalyst hydraulic performance decline.
Summary of the invention
The process for reactivation that the purpose of this invention is to provide a kind of fischer-tropsch synthetic catalyst is to solve the problem that is prone to overtemperature when fischer-tropsch synthetic catalyst activates.
The method that invention provides comprises:
(1) fischer-tropsch synthetic catalyst to be activated contacts with inert gas that hydrogen content is not more than 5 volume % under less than or equal to 240 ℃, and be 0.5～48h time of contact;
(2) fischer-tropsch synthetic catalyst after processing through step (1) contacts with inert gas that hydrogen content is not more than 5 volume % under greater than 240 ℃ to 410 ℃, time of contact 2～48h;
(3) fischer-tropsch synthetic catalyst after processing through step (2), contact with pure hydrogen under 380～410 ℃, time of contact 2～48h.
In a preferred scheme, comprise the following steps:
(1) catalyst to be activated contacts with inert gas that hydrogen content is not more than 5 volume % under 180～240 ℃, and be 0.5～48h time of contact;
(2) catalyst after processing through step (1) contacts with inert gas that hydrogen content is not more than 5 volume % under 240～400 ℃, time of contact 2～48h;
(3) catalyst after processing through step (2), contact with pure hydrogen under 400 ℃, time of contact 2～48h.
In described step (1), (2) and (3) activation process, operating pressure is 0.1～1.0MPa, and gas agent volume ratio is 300～3000; Preferably, operating pressure is 0.1～0.5MPa, and gas agent volume ratio is 500～1000.
Described inert gas not be for can produce reaction to fischer-tropsch synthetic catalyst, and to the gas that priming reaction can not impact, is preferably nitrogen.
Evenly heat up in described step (1) and step (2) activation process, the heating rate of step (1) is less than the heating rate of step (2).
Described in the activation process of step (1) to unstripped gas and speed to exit in methane content analyze, when in speeding to exit, in methane content and unstripped gas, the difference of methane content is greater than 0.5 volume %, be the difference of methane content in the gas of reactor gateway during greater than 0.5 volume %, reaction bed temperature is no more than 240 ℃.Because the residual methylene of Fischer-Tropsch synthesis can react with hydrogen, generate methane, and this exothermic heat of reaction is violent, if this reaction is not controlled, will cause the bed overtemperature.The present invention is undertaken by controlling methane reaction of formation mitigation under the condition that relaxes, and is about to residual methylene total overall reaction and falls, and has avoided again the generation of overheating problem.
Described fischer-tropsch synthetic catalyst is fixed bed FischerTropsch synthesis catalyst, is Co based Fischer-Tropsch synthesis catalyst and/or iron-base fischer-tropsch synthesis catalyst.
Adopt the method for the invention to carry out activation process to fischer-tropsch synthetic catalyst, avoided overtemperature, the fischer-tropsch synthetic catalyst performance after activation can be recovered preferably.
The specific embodiment
The following examples will be further described method provided by the invention, but not thereby limiting the invention.
In embodiment, the trade names of fischer-tropsch synthetic catalyst used are RTF-2, are produced by China Petrochemical Industry's catalyst Chang Ling branch company.Embodiment adopts single tube fixed bed Fischer-Tropsch synthetic test equipment, and the fischer-tropsch synthetic catalyst loading amount is 800ml, and fischer-tropsch synthetic catalyst dilutes without inert ceramic balls, and the reactor heat-obtaining adopts the mode of drum heat-obtaining.Fischer-tropsch synthetic catalyst to be generated in test is the catalyst after 1000h that turned round under the Fischer-Tropsch synthesis condition on this device, its Fischer-Tropsch synthetic operation condition is 210 ℃ of mean temperatures, pressure 2.5MPa, air speed 500h
-1, H
2/ CO raw materials components mole ratio 2, recycle ratio 13.Activity data after fischer-tropsch synthetic catalyst initial activity and running 1000h sees Table 1.
Reactivity worth after table 1 catalyst runs initial stage and 1000h
| Catalyst runs 24h | Catalyst runs 1000h | |
| The CO conversion ratio, mol% | 88.23 | 86.56 |
| CH 4Selectively, mol% | 7.91 | 8.50 |
| C 5+ selective, mol% | 87.68 | 86.62 |
Embodiment 1
Through following steps, reclaimable catalyst is processed respectively:
(1) nitrogen take hydrogen content as 2 volume % is processed fischer-tropsch synthetic catalyst to be generated, and operating condition is: 210 ℃ of temperature, pressure 0.5MPa, air speed 500h
-1, processing time 6h.
(2) heating rate with 10 ℃/h rises to 225 ℃ with temperature, at this temperature, fischer-tropsch synthetic catalyst is carried out constant temperature and processes 6h, and other operating conditions are constant.
(3) heating rate with 10 ℃/h rises to 240 ℃ with temperature, and the difference of analysis reactor gateway methane content is less than 0.5 volume %.
(4) heating rate with 30 ℃/h rises to 400 ℃ with temperature, at this temperature, catalyst is carried out constant temperature and processes 12h, and other operating conditions are constant.
(5) nitrogen is withdrawn from, increased hydrogen flowing quantity to air speed and reach 500h
-1, with pure hydrogen, catalyst is processed, processing time 12h, other operating conditions are constant.
Fischer-tropsch synthetic catalyst after processing through abovementioned steps is introduced synthesis gas at 160 ℃ again, and at 210 ℃ of mean temperatures, pressure 2.5MPa, air speed 500h
-1, H
2Investigate its reactivity worth under the operating condition of/CO raw materials components mole ratio 2, recycle ratio 13, see Table 2.
Fischer-tropsch synthetic catalyst performance after table 2 activation
| The CO conversion ratio, mol% | 89.48 |
| CH 4Selectively, mol% | 8.01 |
| C 5+ selective, mol% | 87.59 |
In the present embodiment catalyst activation process, obviously fluctuation and overheating problem do not appear in the fischer-tropsch synthetic catalyst bed temperature.Can be found out by table 1 and table 2, by activation method of the present invention, fischer-tropsch synthetic catalyst be activated, after activation, the fischer-tropsch synthetic catalyst performance is near fresh dose of performance.
Comparative Examples 1
Be in the pure hydrogen atmosphere of 100 volume % at hydrogen content, heat up from room temperature to 400 ℃ with the heating rate of 20 ℃/h, prepare under the condition of 400 ℃, catalyst to be carried out activation process.Other operating conditions are: pressure 0.5MPa, air speed 500h
-1
When bed temperature rose to 223 ℃, overheating problem appearred in beds, and bed maximum temperature point is 433 ℃, this moment analysis reactor gateway methane content, the reactor inlet methane content is 0 volume %, the outlet methane content is 22.3 volume %.Explanation the reaction of methane has occured in reactor to generate, and this exothermic heat of reaction is violent, has caused the bed overtemperature under this operating mode.After overtemperature, bed temperature descends naturally, continues to be warming up to 400 ℃ according to former heating rate afterwards, and carries out 24h constant temperature and process at this temperature.
Catalyst after processing through abovementioned steps is introduced synthesis gas at 160 ℃ again, and at 210 ℃ of mean temperatures, pressure 2.5MPa, air speed 500h
-1, H2/CO raw materials components mole ratio 2, recycle ratio 13 operating condition under investigate its reactivity worth, see Table 3.
Table 3 activation rear catalyst performance
| The CO conversion ratio, mol% | 60.63 |
| CH 4Selectively, mol% | 13.25 |
| C 5+ selective, mol% | 72.36 |
As can be seen from Table 3, by method in Comparative Examples, fischer-tropsch synthetic catalyst is carried out activation process, the catalyst performance after activation illustrates when adopting this activation method that catalyst is processed catalyst has been caused infringement far below activation procatalyst performance.
Claims (6)
1. the process for reactivation of a fischer-tropsch synthetic catalyst comprises:
(1) fischer-tropsch synthetic catalyst to be activated contacts with inert gas that hydrogen content is not more than 5 volume % under less than or equal to 240 ℃, and be 0.5～48h time of contact; When in the gas of reactor gateway, the difference of methane content was greater than 0.5 volume %, reaction bed temperature was no more than 240 ℃;
(2) fischer-tropsch synthetic catalyst after processing through step (1) contacts with inert gas that hydrogen content is not more than 5 volume % under greater than 240 ℃ to 410 ℃, time of contact 2～48h;
(3) fischer-tropsch synthetic catalyst after processing through step (2), contact with pure hydrogen under 380～410 ℃, time of contact 2～48h;
In step (1), (2) and (3) activation process, operating pressure is 0.1～1.0MPa, and gas agent volume ratio is 300～3000;
Described fischer-tropsch synthetic catalyst is fixed bed FischerTropsch synthesis catalyst.
2. in accordance with the method for claim 1, it is characterized in that, comprising:
(1) fischer-tropsch synthetic catalyst to be activated contacts with inert gas that hydrogen content is not more than 5 volume % under 180～240 ℃, and be 0.5～48h time of contact;
(2) fischer-tropsch synthetic catalyst after processing through step (1) contacts with inert gas that hydrogen content is not more than 5 volume % under greater than 240 to 400 ℃, time of contact 2～48h;
(3) fischer-tropsch synthetic catalyst after processing through step (2), contact with pure hydrogen under 400 ℃, time of contact 2～48h.
3. in accordance with the method for claim 1, it is characterized in that, in step (1), (2) and (3) activation process, operating pressure is 0.1～0.5MPa, and gas agent volume ratio is 500～1000.
4. according to the described method of claim 1 or 2, it is characterized in that, described inert gas is nitrogen.
5. according to the described method of claim 1 or 2, it is characterized in that, evenly heat up in step (1) and step (2) activation process, the heating rate of step (1) is less than the heating rate of step (2).
6. according to the described method of claim 1 or 2, it is characterized in that, described fischer-tropsch synthetic catalyst is Co based Fischer-Tropsch synthesis catalyst and/or iron-base fischer-tropsch synthesis catalyst.
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| CN103846110B (en) * | 2012-12-03 | 2016-06-29 | 中国石油化工股份有限公司 | The activation method of a kind of fischer-tropsch synthetic catalyst and application thereof |
| CN106552632B (en) * | 2015-09-30 | 2019-04-16 | 神华集团有限责任公司 | A kind of restoring method of Fischer-Tropsch synthetic iron-based catalyst |
| CN107149948B (en) * | 2016-03-02 | 2020-04-21 | 神华集团有限责任公司 | Reduction method of iron-based catalyst for Fischer-Tropsch synthesis |
| GB201614363D0 (en) * | 2016-08-23 | 2016-10-05 | Bp Plc | Fischer-tropsch catalyst performance enhancement process |
| CN107790195B (en) * | 2016-09-05 | 2020-07-17 | 神华集团有限责任公司 | Reduction method of iron-based Fischer-Tropsch catalyst |
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| CN1562484A (en) * | 2004-03-19 | 2005-01-12 | 中国科学院山西煤炭化学研究所 | Method for deoxidizing iron base catalyst of Fisher-Tropsch synthesis in slurry bed |
| CN101703937A (en) * | 2009-09-29 | 2010-05-12 | 武汉凯迪科技发展研究院有限公司 | Method for regenerating cobalt-base catalyst for slurry-phase Fischer-Tropsch synthesis |
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| CN1562484A (en) * | 2004-03-19 | 2005-01-12 | 中国科学院山西煤炭化学研究所 | Method for deoxidizing iron base catalyst of Fisher-Tropsch synthesis in slurry bed |
| CN101703937A (en) * | 2009-09-29 | 2010-05-12 | 武汉凯迪科技发展研究院有限公司 | Method for regenerating cobalt-base catalyst for slurry-phase Fischer-Tropsch synthesis |
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