CN102371189A - Reactivation method for Fishcer-Tropshc synthesis catalyst - Google Patents
Reactivation method for Fishcer-Tropshc synthesis catalyst Download PDFInfo
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- CN102371189A CN102371189A CN2010102571979A CN201010257197A CN102371189A CN 102371189 A CN102371189 A CN 102371189A CN 2010102571979 A CN2010102571979 A CN 2010102571979A CN 201010257197 A CN201010257197 A CN 201010257197A CN 102371189 A CN102371189 A CN 102371189A
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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 fischer-tropsch synthetic catalyst.
Background technology
The fixed bed Fischer-Tropsch is synthetic because its advantage simple to operate, that the heavy hydrocarbon yield is high 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, selectivity all can decrease, and after the fischer-tropsch synthetic catalyst activity is reduced to a certain degree, need handle to improve catalyst performance 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 processing 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 this method is under Fischer-Tropsch synthetic operation pattern, reduces the content of CO in the unstripped gas gradually, to reactor outlet H
2/ CO the regular hour of under this operating mode, turning round, makes catalyst performance obtain part and recovers than surpassing 10: 1.
US6486220 discloses a kind of activation method of fischer-tropsch synthetic catalyst, and this method is that reclaimable catalyst carries out activation processing in containing the atmosphere of steam.The activation processing 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 this method is taked in interior hydrogen atmosphere, catalyst to be handled including ammonia or weak organic acid, and the catalyst processed performance 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 performance to descend.
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 prone to the problem of overtemperature when solving the fischer-tropsch synthetic catalyst activation.
The method that invention is provided comprises:
(1) fischer-tropsch synthetic catalyst to be activated is contacting with the inert gas that hydrogen content is not more than 5 volume % down smaller or equal to 240 ℃, and be 0.5～48h time of contact;
(2) fischer-tropsch synthetic catalyst after handling through step (1) is contacting with the inert gas that hydrogen content is not more than 5 volume % down greater than 240 ℃ to 410 ℃, time of contact 2～48h;
(3) fischer-tropsch synthetic catalyst after handling through step (2) contacts with pure hydrogen down at 380～410 ℃, time of contact 2～48h.
In a preferred scheme, may further comprise the steps:
(1) catalyst to be activated contacts with the inert gas that hydrogen content is not more than 5 volume % down at 180～240 ℃, and be 0.5～48h time of contact;
(2) through step (1) catalyst processed, contact with the inert gas that hydrogen content is not more than 5 volume % down at 240～400 ℃, time of contact 2～48h;
(3) through step (2) catalyst processed, contact with pure hydrogen down at 400 ℃, time of contact 2～48h.
Operating pressure is 0.1～1.0MPa in said step (1), (2) and (3) activation process, and gas agent volume ratio is 300～3000; Preferably, operating pressure is 0.1～0.5MPa, and gas agent volume ratio is 500～1000.
Said 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 said step (1) and step (2) activation process, the heating rate of step (1) is less than the heating rate of step (2).
Said in the activation process of step (1) to unstripped gas with speed to exit in methane content analyze; When the difference of methane content is greater than 0.5 volume % in methane content and the unstripped gas in speeding to exit; 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 carries out through control methane reaction of formation mitigation under the condition that relaxes, and is about to residual methylene total overall reaction and falls, and has avoided the generation of overheating problem again.
Said fischer-tropsch synthetic catalyst is the fixed bed fischer-tropsch synthetic catalyst, is Co based Fischer-Tropsch synthesis catalyst and/or iron-base fischer-tropsch synthesis catalyst.
Adopt the method for the invention that fischer-tropsch synthetic catalyst is carried out activation processing, avoided overtemperature, the fischer-tropsch synthetic catalyst performance after the activation can be recovered preferably.
The specific embodiment
Following embodiment will further explain method provided by the invention, but therefore not limit the present invention.
The trade names of used fischer-tropsch synthetic catalyst are RTF-2 among the embodiment, are produced by catalyst Chang Ling branch company of China Petrochemical Industry.Embodiment adopts single tube fixed bed Fischer-Tropsch synthetic test device, 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 the test is the catalyst behind the 1000h that on this device, under the Fischer-Tropsch synthesis condition, turned round, and 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 behind fischer-tropsch synthetic catalyst initial activity and the running 1000h is seen table 1.
Reactivity worth behind table 1 catalyst runs initial stage and the 1000h
| Catalyst runs 24h | Catalyst runs 1000h | |
| The CO conversion ratio, mol% | 88.23 | 86.56 |
| CH 4Selectivity, mol% | 7.91 | 8.50 |
| C 5+ selectivity, mol% | 87.68 | 86.62 |
Embodiment 1
Through following steps reclaimable catalyst is handled respectively:
(1) be that the nitrogen of 2 volume % is handled fischer-tropsch synthetic catalyst to be generated with hydrogen content, 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, under this temperature, fischer-tropsch synthetic catalyst is carried out constant temperature and handles 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, under this temperature, catalyst is carried out constant temperature and handles 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 handled, processing time 12h, other operating conditions are constant.
Through the fischer-tropsch synthetic catalyst after the abovementioned steps processing, introduce 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 4Selectivity, mol% | 8.01 |
| C 5+ selectivity, mol% | 87.59 |
In 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, through activation method according to the invention fischer-tropsch synthetic catalyst carried out activation, the fischer-tropsch synthetic catalyst performance is near fresh dose of performance after the activation.
Comparative Examples 1
At hydrogen content is in the pure hydrogen atmosphere of 100 volume %, heats up to 400 ℃ from room temperature with the heating rate of 20 ℃/h, prepares under 400 ℃ condition, catalyst to be carried out activation processing.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 taken place in the reactor to generate, and this exothermic heat of reaction is violent, has caused the bed overtemperature under this operating mode.Bed temperature descends naturally behind the overtemperature, continues to be warming up to 400 ℃ according to former heating rate afterwards, and under this temperature, carries out 24h constant temperature and handle.
Through the abovementioned steps catalyst processed, introduce 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 4Selectivity, mol% | 13.25 |
| C 5+ selectivity, mol% | 72.36 |
Can be found out by table 3, through method in the Comparative Examples fischer-tropsch synthetic catalyst carried out activation processing, the catalyst activated performance is explained when adopting this activation method that catalyst is handled catalyst has been caused infringement far below activation procatalyst performance.
Claims (9)
1. the process for reactivation of a fischer-tropsch synthetic catalyst comprises:
(1) fischer-tropsch synthetic catalyst to be activated is contacting with the inert gas that hydrogen content is not more than 5 volume % down smaller or equal to 240 ℃, and be 0.5～48h time of contact;
(2) fischer-tropsch synthetic catalyst after handling through step (1) is contacting with the inert gas that hydrogen content is not more than 5 volume % down greater than 240 ℃ to 410 ℃, time of contact 2～48h;
(3) fischer-tropsch synthetic catalyst after handling through step (2) contacts with pure hydrogen down at 380～410 ℃, time of contact 2～48h.
2. according to the described method of claim 1, it is characterized in that, comprising:
(1) fischer-tropsch synthetic catalyst to be activated contacts with the inert gas that hydrogen content is not more than 5 volume % down at 180～240 ℃, and be 0.5～48h time of contact;
(2) fischer-tropsch synthetic catalyst after handling through step (1) contacts with the inert gas that hydrogen content is not more than 5 volume % down at 240～400 ℃, time of contact 2～48h;
(3) fischer-tropsch synthetic catalyst after handling through step (2) contacts with pure hydrogen down at 400 ℃, time of contact 2～48h.
3. according to claim 1 or 2 described methods, it is characterized in that operating pressure is 0.1～1.0MPa in step (1), (2) and (3) activation process, gas agent volume ratio is 300～3000.
4. according to the described method of claim 3, it is characterized in that operating pressure is 0.1～0.5MPa in step (1), (2) and (3) activation process, gas agent volume ratio is 500～1000.
5. according to claim 1 or 2 described methods, it is characterized in that said inert gas is a nitrogen.
6. according to claim 1 or 2 described methods, 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).
7. according to claim 1 or 2 described methods, it is characterized in that when the difference of methane content was greater than 0.5 volume % in the gas of step (1) reactor gateway, reaction bed temperature was no more than 240 ℃.
8. according to claim 1 or 2 described methods, it is characterized in that said fischer-tropsch synthetic catalyst is the fixed bed fischer-tropsch synthetic catalyst.
9. according to claim 1 or 2 described methods, it is characterized in that said fischer-tropsch synthetic catalyst is Co based Fischer-Tropsch synthesis catalyst and/or iron-base fischer-tropsch synthesis catalyst.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103846110A (en) * | 2012-12-03 | 2014-06-11 | 中国石油化工股份有限公司 | Activation method and application of Fischer-Tropsch synthesis catalyst |
| CN106552632A (en) * | 2015-09-30 | 2017-04-05 | 神华集团有限责任公司 | A kind of method of reducing of Fischer-Tropsch synthetic iron-based catalyst |
| CN107149948A (en) * | 2016-03-02 | 2017-09-12 | 神华集团有限责任公司 | A kind of restoring method of Fischer-Tropsch synthetic iron-based catalyst |
| CN107790195A (en) * | 2016-09-05 | 2018-03-13 | 神华集团有限责任公司 | A kind of restoring method of iron-base fischer-tropsch catalyst |
| CN110022980A (en) * | 2016-08-23 | 2019-07-16 | 英国石油有限公司 | Enhance the method for Fischer-Tropsch catalyst performance |
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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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Patent Citations (3)
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| WO2004096434A1 (en) * | 2003-03-31 | 2004-11-11 | Exxonmobil Chemical Patents Inc. | Catalyst activation method and activated catalyst |
| 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 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103846110A (en) * | 2012-12-03 | 2014-06-11 | 中国石油化工股份有限公司 | Activation method and application of Fischer-Tropsch synthesis catalyst |
| 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 |
| CN106552632A (en) * | 2015-09-30 | 2017-04-05 | 神华集团有限责任公司 | A kind of method of reducing of Fischer-Tropsch synthetic iron-based catalyst |
| 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 |
| CN107149948A (en) * | 2016-03-02 | 2017-09-12 | 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 |
| CN110022980A (en) * | 2016-08-23 | 2019-07-16 | 英国石油有限公司 | Enhance the method for Fischer-Tropsch catalyst performance |
| CN110022980B (en) * | 2016-08-23 | 2023-07-14 | 英国石油有限公司 | Process for enhancing the performance of a Fischer-Tropsch catalyst |
| CN107790195A (en) * | 2016-09-05 | 2018-03-13 | 神华集团有限责任公司 | A kind of restoring method of iron-base fischer-tropsch catalyst |
| 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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