CN103769244A - Reduction method of cobalt-based Fischer-Tropsch synthesis catalyst - Google Patents
Reduction method of cobalt-based Fischer-Tropsch synthesis catalyst Download PDFInfo
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- CN103769244A CN103769244A CN201210408261.8A CN201210408261A CN103769244A CN 103769244 A CN103769244 A CN 103769244A CN 201210408261 A CN201210408261 A CN 201210408261A CN 103769244 A CN103769244 A CN 103769244A
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Abstract
The invention discloses a reduction method of a cobalt-based Fischer-Tropsch synthesis catalyst. The reduction method comprises following steps: gas replacement; catalyst drying; reduction processes before passivation; passivation processes; and reduction processed after passivation; wherein the reduction processes before passivation are performed in the presence of microwave. The reduction method is capable of increasing activity and stability of the cobalt-based Fischer-Tropsch synthesis catalyst, reducing initial activity of the cobalt-based Fischer-Tropsch synthesis catalyst, and realizing smooth operation of Fischer-Tropsch synthetic apparatuses.
Description
Technical field
The present invention relates to a kind of method of reducing of Co based Fischer-Tropsch synthesis catalyst.
Background technology
Synthesis gas be carbon monoxide and hydrogen to be converted into high-value product be well-known, applied for many years industrial.Typical technique comprises: methyl alcohol is synthetic, and higher alcohol is synthetic, and hydroformylation and Fischer-Tropsch are synthetic.Fischer-Tropsch is synthetic refers to that synthesis gas catalyzes and synthesizes the reaction of liquid hydrocarbon fuel on catalyst.Along with the exhaustion day by day of petroleum resources, be more subject to the attention of countries in the world with Fischer-Tropsch synthesis prepare liquid fuel.Catalyst is one of key technology of Fischer-Tropsch synthesis.In the research of the fischer-tropsch catalysts of nearly 80 years, people have found that Fe, Co and Ru etc. are the effective active components of fischer-tropsch catalysts, activity, the stability of various auxiliary elements to fischer-tropsch catalysts such as Zr, K and Cu play an important role, and the carrier of catalyst is with unformed SiO
2, TiO
2and Al
2o
3be main.How active component, metal promoter and carrier are carried out to effective and reasonable collocation, prepare there is high activity, the fischer-tropsch synthetic catalyst of high selectivity and high stability is the focus of research.Use cobalt-base catalyst can not only generate to greatest extent heavy hydrocarbon, and cobalt-base catalyst carbon distribution tendency is low, active high, therefore take cobalt-base catalyst as basic research significant.
Employing infusion process on suitable carrier, after forming catalyst precursors, is dried one or more metal impregnations, then roasting under oxygen-containing atmosphere.Predecessor is in reducing gases subsequently, and typical case comprises under the existence of hydrogen, is activated by high temperature reduction.US5292705 is disclosed, in the time that liquid hydrocarbon exists, and by contacting with hydrogen, activating catalyst.US4492774, US4585798, US4088671, US4670414 and EP0253924 are disclosed by the method for reducing/oxidizing/reduction cyclic activation Co catalysts, can improve the activity of F-T synthetic reaction.All oxidation/reduction/oxidations of describing in above-mentioned patent or reducing/oxidizing/reduction circulation is used oxygen-containing gas at high temperature process solid catalyst and carry out mostly, may cause forming the such as Co of oxide of most stable
3o
4generation, reduce the content of active component in catalyst, in addition, also to strictly control the exothermicity of oxidation reaction and guarantee water partial pressure low between reduction period in order to avoid the sintering of cobalt.
European patent EP 0533228 discloses a kind of Co/Zr/Al
2o
3(SiO
2or TiO
2) method of reducing of catalyst.Being specially at pressure is under the condition of 100 ~ 350 ℃ of 1-10mbar and temperature, with hydrogen-containing gas (0 ~ 70%H
2/ inert gas, V/V) reducing catalyst, H in hydrogen-containing gas when reduction
2concentration and air speed progressively or increase continuously to guarantee H
2the dividing potential drop of O is lower than 200mbar.
For the synthetic load type cobalt-base catalyst of Fischer-Tropsch, although can improve the activity of catalyst by different method of reducing, but inevitably, in the process of a catalyst rapid deactivation of initial reaction stage ubiquity, then reach active stabilization period, the higher initial activity of activity is also higher often.CN201010221133.3 discloses a kind of method of reducing of Co based Fischer-Tropsch synthesis catalyst, comprises gas displacement and catalyst dry run, reduction process and passivating process.Described passivating process adopts to the mixed air that switches steam or oxygen-bearing organic matter steam and hydrogen in reduction system, steam or the volumetric concentration of oxygen-bearing organic matter steam in gaseous mixture are 1-5%, gaseous mixture air speed is 500～2000h-1, passivation temperature is 180～280 ℃, and passivation time is 4-16h.The method effectively reduces the initial activity of catalyst, is that Fischer-Tropsch synthesizer can move stably, but this catalyst still needs further raising in the activity of Fischer-Tropsch synthesis stationary phase, and product distributes and needs to be optimized.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method of reducing of Co based Fischer-Tropsch synthesis catalyst.This method of reducing not only can improve the activity stability of catalyst, and can reduce the initial activity of catalyst, and Fischer-Tropsch synthesizer can be moved stably.
The method of reducing of Co based Fischer-Tropsch synthesis catalyst of the present invention comprises reduction process after gas displacement and catalyst dry run, passivation pre reduction process, passivating process and passivation, and described passivation pre reduction process is to carry out under the effect of microwave.
The microwave frequency adopting in the inventive method is 3000MHz～10000MHz.
Gas displacement described in the inventive method and catalyst dry run adopt and pass into inert gas in reduction systems, and inert gas volume space velocity is 500 ~ 2000h
-1, and the pressure of reduction system is maintained to 0.1 ~ 3.0MPa, temperature rises to 250 ~ 450 ℃, dry 4-16h.
After passivation pre reduction process described in the inventive method and passivation, reduction process adopts and first in reduction system, switches H
2volumetric concentration is the H of 1%-10%
2with the gaseous mixture of inert gas, volume space velocity is 1000 ~ 5000h
-1, after temperature rises to 250 ~ 450 ℃, improve gradually H in gaseous mixture
2above reduction of concentration to 90%, the passivation pre reduction time is 5-60h, after passivation, the recovery time is 4 ~ 10h.
Passivating process described in the inventive method adopts in reduction system and switches the hydrogen mixed air that contains water vapour or oxygen-bearing organic matter steam, water vapour or the volumetric concentration of oxygen-bearing organic matter steam in gaseous mixture are 1%-5%, and gaseous mixture volume air speed is 500 ~ 2000h
-1, passivation temperature is 180 ~ 280 ℃, passivation time is 4-16h.Described water vapour or the volumetric concentration of oxygen-bearing organic matter steam in gaseous mixture are 2%-4%, and gaseous mixture volume air speed is 500 ~ 1500 h
-1, passivation temperature is 200 ~ 250 ℃, passivation time is 8-12h.Described oxygen-bearing organic matter steam comprises one or more in methanol steam, alcohol vapour, propyl alcohol steam, oxirane steam, acetone steam, expoxy propane steam, particular methanol steam.
Load type cobalt-base fischer-tropsch synthetic catalyst described in the inventive method, take Co as active component, take one or more in Zr, Hf, Ce and Th, Pt, Ru, Ni, Mo and W as auxiliary agent, with ZrO
2, TiO
2, SiO
2and Al
2o
3one or more are mixed into carrier.
Compared with prior art, the inventive method Co based Fischer-Tropsch synthesis catalyst method of reducing tool has the following advantages:
1, the reduction process after reduction process, passivating process and the passivation under microwave action of the present invention cooperatively interacts, can improve the activity of Co based Fischer-Tropsch synthesis catalyst, reduce the initial activity of catalyst in Fischer-Tropsch synthesis process simultaneously, make the Fischer-Tropsch synthesis device can even running;
2, method of reducing of the present invention, in reduction process before passivation, use microwave technology, microwave can produce and interact with the active component of catalyst, under this effect, carry out the reduction of active component, can exert an influence to the physical property such as reduction degree, decentralization of active component, result of the test shows, the interaction between hydrogen, microwave, active component has obviously improved the activity of catalyst;
3, in reduction process, add the catalyst after microwave treatment, show more excellent selectivity of product in Fischer-Tropsch building-up process, methane selectively reduces, C
5 +selective raising.
The specific embodiment
Further illustrate process and the effect of the inventive method below in conjunction with embodiment.
Example 1
Filling load type cobalt-base fischer-tropsch synthetic catalyst 20%Co0.8%Pt3%Zr/SiO
2(Wt.), under normal pressure, pass into inert gas, air speed is 500h
-1, at normal temperatures and pressures by complete the air displacement in reduction system, then the pressure of reduction system is maintained to 0.1MPa with inert gas, be warming up to 300 ℃ from room temperature with 1 ℃/min, after dry 12h, be cooled to 120 ℃.The H that switching concentration is 5%
2with the gaseous mixture of inert gas, air speed is 2000h
-1, heat up 300 ℃ with 1 ℃/min from 120 ℃, then improve gradually H in gaseous mixture
2concentration to 90% more than, reductase 12 4h under the effect that is 3000MHz in microwave frequency, then cools 120 ℃.Pass into the hydrogen containing 2% water vapour, air speed is 500 h
-1time, be warming up to 200 ℃ from 120 ℃ with 1 ℃/min, maintain after 12h, be cooled to 120 ℃.The H that switching concentration is 5%
2with the gaseous mixture of inert gas, air speed is 2000h
-1, be warming up to 300 ℃ from 120 ℃ with 1 ℃/min, then improve gradually H in gaseous mixture
2concentration to 90% more than, reduction 10h, be then cooled to 40 ℃.Switch inert gas, and maintain 40 ℃.After reduction, under the condition contacting with oxygen, the catalyst having reduced is poured in liquid wax stopping.
Then the above-mentioned liquid wax that contains activating catalyst is poured in 1L continuous-flow stirred-tank reactor (CSPR) into reaction condition: reaction temperature is 220 ℃, 2.5Nm
3/ h/kg cat., pressure is 2.0MPa, H
2/ CO=2(mol ratio).Reaction effluent is collected by hot trap, cold-trap respectively.The conversion ratio of catalyst, methane selectively, C
5 +the results are shown in Table 1 for selective and 200h stability test.
Example 2
Filling load type cobalt-base fischer-tropsch synthetic catalyst 20%Co1%Ni3%Zr/TiO
2(Wt.), under normal pressure, pass into inert gas, air speed is 1500 h
-1time, at normal temperatures and pressures by complete the air displacement in reduction system, then the pressure of reduction system is raised to 1.0MPa with inert gas, be warming up to 400 ℃ from room temperature with 3 ℃/min, after dry 8h, be cooled to 120 ℃.The H that switching concentration is 5%
2with the gaseous mixture of inert gas, air speed is 4000h
-1, be warming up to 400 ℃ from 120 ℃ with 3 ℃/min, then improve gradually H in gaseous mixture
2concentration to more than 90%, under the effect that is 9000MHz in microwave frequency, reduce 8h, then lower the temperature 120 ℃.The hydrogen that passes into the methanol steam that contains 4%, air speed is 1500 h
-1time, be warming up to 250 ℃ from room temperature with 3 ℃/min, maintain after 8h, be cooled to 120 ℃.The H that switching concentration is 5%
2with the gaseous mixture of inert gas, air speed 4000h
-1, be warming up to 400 ℃ from 120 ℃ with 3 ℃/min, then improve gradually H in gaseous mixture
2concentration to more than 90%, reduction 4h, is then cooled to 40 ℃.Switch inert gas, and maintain 40 ℃.After reduction, under the condition contacting with oxygen, the catalyst having reduced is poured in liquid wax stopping.
Evaluation method is with embodiment 1, the conversion ratio of catalyst, methane selectively, C
5 +the results are shown in Table 1 for selective and 200h stability test.
Example 3
Filling load type cobalt-base fischer-tropsch synthetic catalyst 20%Co0.05%Ru3%Zr/Al
2o
3(Wt.), under normal pressure, pass into inert gas, air speed is 1000h
-1time, at normal temperatures and pressures by complete the air displacement in reduction system, then the pressure of reduction system is raised to 0.5MPa with inert gas, be warming up to 350 ℃ from room temperature with 2 ℃/min, after dry 10h, be cooled to 120 ℃.The H that switching concentration is 5%
2with the gaseous mixture of inert gas, air speed is 3000h
-1, be warming up to 350 ℃ from 120 ℃ with 2 ℃/min, then improve gradually H in gaseous mixture
2concentration to more than 90%, under the effect that is 6000MHz in microwave frequency, reduce 16h, then 120 ℃ of cold coolings.The hydrogen that passes into the alcohol vapour that contains 3%, air speed is 1000 h
-1time, be warming up to 220 ℃ from room temperature with 2 ℃/min, maintain after 10h, be cooled to 120 ℃.The H that switching concentration is 5%
2with the gaseous mixture of inert gas, air speed is 3000h
-1, be warming up to 350 ℃ from 120 ℃ with 2 ℃/min, then improve gradually H in gaseous mixture
2concentration to more than 90%, reduction 8h, is then cooled to 40 ℃.Switch inert gas, and maintain 40 ℃.After reduction, under the condition contacting with oxygen, the catalyst having reduced is poured in liquid wax stopping.
Evaluation method is with embodiment 1, the conversion ratio of catalyst, methane selectively, C
5 +the results are shown in Table 1 for selective and 200h stability test.
Comparative example
Be without microwave action in the reduction process before passivation with embodiment 1.Evaluation method is with embodiment 1, the conversion ratio of catalyst, methane selectively, C
5 +the results are shown in Table 1 for selective and 200h stability test.
The reactivity worth of table 1 catalyst
Claims (10)
1. the method for reducing of a Co based Fischer-Tropsch synthesis catalyst, comprise reduction process after gas displacement and catalyst dry run, passivation pre reduction process, passivating process and passivation, it is characterized in that: described passivation pre reduction process is to carry out under the effect of microwave.
2. catalyst according to claim 1, is characterized in that: the microwave frequency of employing is 3000MHz～10000MHz.
3. catalyst according to claim 1, is characterized in that: described gas displacement and catalyst dry run adopt and pass into inert gas in reduction system, and inert gas volume space velocity is 500 ~ 2000h
-1, and the pressure of reduction system is maintained to 0.1 ~ 3.0Mpa, temperature rises to 250 ~ 450 ℃, dry 4-16h.
4. catalyst according to claim 1, is characterized in that: after described passivation pre reduction process and passivation, reduction process adopts and first in reduction system, switches H
2volumetric concentration is the H of 1%-10%
2with the gaseous mixture of inert gas, volume space velocity is 1000 ~ 5000h
-1, after temperature rises to 250 ~ 450 ℃, improve gradually H in gaseous mixture
2above reduction of concentration to 90%.
5. according to the catalyst described in claim 1 or 4, it is characterized in that: the passivation pre reduction time is 5-60h, after passivation, the recovery time is 4 ~ 10h.
6. catalyst according to claim 1, it is characterized in that: described passivating process adopts in reduction system and switches the hydrogen mixed air that contains water vapour or oxygen-bearing organic matter steam, water vapour or the volumetric concentration of oxygen-bearing organic matter steam in gaseous mixture are 1%-5%, and gaseous mixture volume air speed is 500 ~ 2000h
-1, passivation temperature is 180 ~ 280 ℃, passivation time is 4-16h.
7. catalyst according to claim 6, is characterized in that: described water vapour or the volumetric concentration of oxygen-bearing organic matter steam in gaseous mixture are 2%-4%, and gaseous mixture volume air speed is 500 ~ 1500 h
-1, passivation temperature is 200 ~ 250 ℃, passivation time is 8-12h.
8. catalyst according to claim 6, is characterized in that: described oxygen-bearing organic matter steam comprises one or more in methanol steam, alcohol vapour, propyl alcohol steam, oxirane steam, acetone steam, expoxy propane steam, particular methanol steam.
9. catalyst according to claim 8, is characterized in that: described oxygen-bearing organic matter steam is methanol steam.
10. method of reducing according to claim 1, is characterized in that: described Co based Fischer-Tropsch synthesis catalyst, and take Co as active component, take one or more in Zr, Hf, Ce and Th, Pt, Ru, Ni, Mo and W as auxiliary agent, with ZrO
2, TiO
2, SiO
2and Al
2o
3one or more are carrier.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105233884A (en) * | 2014-07-11 | 2016-01-13 | 中国石油化工股份有限公司 | Cryogenic passivation pretreatment process for nickel-based catalyst |
| CN113694954A (en) * | 2021-08-31 | 2021-11-26 | 安徽大学 | Preparation method and application of microwave in-situ rapid synthesis heteroatom functionalized supported metal catalyst |
| CN115364870A (en) * | 2022-09-29 | 2022-11-22 | 中国科学院上海高等研究院 | Catalyst for directly synthesizing high-carbon olefin product by synthesis gas one-step method, preparation method and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105233884A (en) * | 2014-07-11 | 2016-01-13 | 中国石油化工股份有限公司 | Cryogenic passivation pretreatment process for nickel-based catalyst |
| CN113694954A (en) * | 2021-08-31 | 2021-11-26 | 安徽大学 | Preparation method and application of microwave in-situ rapid synthesis heteroatom functionalized supported metal catalyst |
| CN115364870A (en) * | 2022-09-29 | 2022-11-22 | 中国科学院上海高等研究院 | Catalyst for directly synthesizing high-carbon olefin product by synthesis gas one-step method, preparation method and application thereof |
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| CN103769244B (en) | 2016-03-30 |
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