CN103071543B - Reduction method for iron-based catalyst for Fischer-Tropsch synthesis in fixed bed - Google Patents
Reduction method for iron-based catalyst for Fischer-Tropsch synthesis in fixed bed Download PDFInfo
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- CN103071543B CN103071543B CN201310043997.4A CN201310043997A CN103071543B CN 103071543 B CN103071543 B CN 103071543B CN 201310043997 A CN201310043997 A CN 201310043997A CN 103071543 B CN103071543 B CN 103071543B
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Abstract
The invention discloses a reduction method for an iron-based catalyst for Fischer-Tropsch synthesis in a fixed bed. The method comprises the following steps: adding the iron-based catalyst into a fixed bed reactor; and introducing gaseous hydrocarbon or mixed gas of hydrogen and gaseous hydrocarbon into the fixed bed reactor for reduction reaction to reduce the iron-based catalyst. The reduction method has the advantages that (1) the reduced catalyst has a little carbon deposit, so the catalyst has high activity and stability; (2) the product selectivity of the catalyst can be effectively modulated, and the selectivity for C5-30 in products is high; and (3) the reduced catalyst has a little carburization, so the catalyst has high wear resistance.
Description
Technical field
The present invention relates to a kind of method of reducing of fixed bed Fischer-Tropsch synthetic iron-based catalyst.
Background technology
Fischer-Tropsch synthesis refers to process synthesis gas being changed under the effect of catalyst into oil product and chemicals.China is the country of the few oil of coal more than.Petroleum resources are relatively less, and for meeting the demand of vehicle fuel and chemicals, China needs a large amount of Imported oil every year.In recent years, the external dependence degree of China's oil, more than 50%, has had a strong impact on national energy security.Adopting is that synthesis gas is prepared in source with coal, then the coal resources of China's rich reserves can be converted into the fuel of very shortage through the process route that Synthetic holography is oil product and chemicals by Fischer-Tropsch synthesis, greatly alleviates national energy security situation.
The catalyst that Fischer-Tropsch synthesis is conventional has iron-based, cobalt-based and ruthenium-based catalyst.Wherein ferrum-based catalyst has cheap, and activity is higher, selective be easy to the advantages such as modulation and be very suitable for heavy industrialization application.The reactor that Fischer-Tropsch synthesis is conventional comprises fixed bed reactors, fluidized-bed reactor and paste state bed reactor.Compared with fixed bed reactors, it is homogeneous that paste state bed reactor has inside reactor temperature, is easy to control, can the more advantage such as catalyst changeout online, simultaneously paste state bed reactor to the requirement of catalyst strength lower than fluidized-bed reactor.Above advantage makes paste state bed reactor be very suitable for heavy industrialization application.
The main component of the unreduced iron-base fischer-tropsch synthesis catalyst of fresh state is α-Fe
2o
3, this thing relative Fischer-Tropsch synthesis process catalyst-free is active.Catalyst needs to reduce in certain atmosphere, by the α-Fe in catalyst
2o
3just catalyst activity can be had after being converted into α-Fe or iron-carbon compound.The reducing condition of catalyst all has obvious impact to the activity of catalyst, selective, stability and abrasion resistance etc.
Chinese patent (200410012199.6) discloses a kind of method of reducing of syrup state bed Fischer Tropsch synthetic catalyst.Be specially with H
2in the atmosphere of/CO=0.5 ~ 2.5, controlling reduction temperature is 200 ~ 350 ° of C, and reaction pressure is reduction 5 ~ 60h under the condition of 0.01 ~ 3.0MPa.
Chinese patent (200710040569.0) discloses a kind of method of reducing of fluidized-bed reactor fused iron catalyst.The method is with hydrogen or synthesis gas (H
2/ CO=10 ~ 40) be reducing atmosphere, reduction temperature controls at 280 ~ 500 ° of C, and the recovery time is in 72h.
Chinese patent (200510026968.2) discloses a kind of industrial reduction method of particle iron-base fischer-tropsch synthesis catalyst.Reduction process control temperature is 260 ~ 450 ° of C, and pressure is 1.5 ~ 5.0MPa, and inlet velocity is 0.15 ~ 0.7m/s, and reducing gas adopts H
2or CO, or H
2with the mist of CO.
Comprehensive above prior art, can find that the preprocess method adopted at present generally all adopts H
2, CO or synthesis gas be reducing atmosphere.Take hydrogen as reducing atmosphere, catalyst is generally reduced to α-Fe, and α-Fe thing is mutually unstable, and after switching to reaction condition, α-Fe thing transforms very soon mutually and is oxidized to Fe
3o
4, or carbonization is Fe
xc, simultaneously with serious carbon distribution, cause the poor catalyst stability after hydrogen reducing, wear resistance is poor.During with CO or synthesis gas for catalyst, catalyst is generally reduced to Fe
3o
4and Fe
xthe mixture of C.Because CO has stronger carbon distribution ability, in reduction process, easily cause the excessive carbon distribution of catalyst and then affect the activity of catalyst.In fixed bed reactors, excess carburizing will cause catalyst generation efflorescence, and bed layer pressure significantly increases, so that cannot proceed reaction.
Summary of the invention
The object of this invention is to provide a kind of method of reducing of fixed bed Fischer-Tropsch synthetic iron-based catalyst, the present invention replaces CO for carbon source with gaseous hydrocarbon, can either make the α-Fe in catalyst
2o
3change Fe into
3o
4and Fe
xc, effectively can suppress excess carburizing and excessive carbon distribution again, makes the catalyst after adopting this method reduction have higher activity and stability, improves C simultaneously
5 ~ 30hydro carbons selective.
The method of reducing of a kind of fixed bed Fischer-Tropsch synthetic iron-based catalyst provided by the present invention, comprises the steps:
Ferrum-based catalyst is added in fixed bed reactors; In described fixed bed reactors, pass into the mist of gaseous hydrocarbon or hydrogen and gaseous hydrocarbon, carry out reduction reaction, namely realize the reduction to described ferrum-based catalyst.
In above-mentioned method of reducing, described ferrum-based catalyst can be made up of Fe, structural promoter, carrier and electronic auxiliary;
The mass ratio of described Fe, described structural promoter, described carrier and described electronic auxiliary can be 100:0.5 ~ 20:5 ~ 40:0.2 ~ 10, specifically can be 100:3 ~ 15:15 ~ 30:1 ~ 6,100:15:30:6,100:8:30:1,100:3:15:1,100:3:20:1 or 100:9:20:3.
In above-mentioned method of reducing, described structural promoter can be at least one in Cu, La, Ce, Cr, Zn, Mn and Mo;
Described carrier can be SiO
2, Al
2o
3or ZrO
2middle at least one;
Described electronic auxiliary can be at least one in Li, Na, K, Rb and Cs.
In above-mentioned method of reducing, described gaseous hydrocarbon can be CH
4, C
2h
4, C
2h
6, C
3h
6, C
3h
8and C
4h
8middle at least one.
In above-mentioned method of reducing, in the mist of described hydrogen and described gaseous hydrocarbon, the mol ratio of described hydrogen and described gaseous hydrocarbon can be 1 ~ 100:1, specifically can be 1 ~ 20:1,10:1 or 20:1.
In above-mentioned method of reducing, the pressure of described reduction reaction can be 0.1 ~ 4.0MPa, specifically can be 0.2MPa, 0.3MPa, 1.0MPa, 2.0MPa, temperature can be 240 ~ 350 ° of C, specifically can be 260 ~ 320 ° of C, 260 ° of C, 280 ° of C, 285 ° of C or 320 ° C, time can be 10 ~ 60h, specifically can be 20 ~ 48h, 20h, 24h, 30h, 36h or 48h, and the programming rate in described reduction reaction can be 5 ~ 20 ° of C/h.
In above-mentioned method of reducing, in described reduction reaction, the air speed of the mist of described gaseous hydrocarbon or described hydrogen and described carburet hydrogen can be 500 ~ 5000h
-1, specifically can be 500 ~ 2000h
-1, 500h
-1or 2000h
-1; Recycle ratio (mol ratio of circulating air and virgin gas) can be 0 ~ 20, specifically can be 0 ~ 10,0,5 or 10.
In above-mentioned method of reducing, before the mist passing into described gaseous hydrocarbon or described hydrogen and gaseous hydrocarbon, described method also comprises pass into the step that hydrogen carries out prereduction in described fixed bed reactors.
In above-mentioned pre-reduction, the air speed passing into described hydrogen can be 500 ~ 5000h
-1, specifically can be 500h
-1or 3000h
-1; Recycle ratio can be 0 ~ 15, specifically can be 5 ~ 15,5 or 15;
The temperature of described prereduction can be 240 ~ 400 ° of C, specifically can be 260 ~ 360 ° of C, 260 ° of C, 360 ° of C, programming rate can be 5 ~ 20 ° of C/h, specifically can be 5 ° of C/h, 10 ° of C/h, constant temperature time can be 1 ~ 48h, specifically can be 6h, 24h, pressure can be 0.1 ~ 4.0MPa, specifically can be 2.0MPa, 3.0MPa.
Compared with prior art, method of reducing tool of the present invention has the following advantages:
(1) catalyst carbon deposition after reduction is few, thus active high, good stability;
(2) can the selectivity of product of effective regulating catalyst, C in product
5 ~ 30selective height;
(3) the catalyst carburizing after reduction is few, and thus antiwear property is strong.
Detailed description of the invention
The experimental technique used in following embodiment if no special instructions, is conventional method.
Material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.
Embodiment 1,
Be loaded in fixed bed reactors by 5g Fischer-Tropsch synthetic iron-based catalyst, catalyst consists of 100Fe/10Ce/5Cu/6K/30SiO
2(for mass ratio).H is passed in fixed bed reactors
2, adjustment reactor pressure is 2.0MPa, and air speed is 3000h
-1, recycle ratio is 5, and reactor rises to constant temperature 6h after 360 ° of C by room temperature with the programming rate of 10 ° of C/h.With 10 ° of C/h, reduction temperature is down to 320 ° of C, reducing atmosphere switches to H
2/ C
2h
4the mist of (mol ratio is 20:1), air speed 3000h
-1, recycle ratio is 5, keeps temperature to be that 320 ° of C reductase 12 0h obtain the ferrum-based catalyst after reducing, be designated as A under this atmosphere.
After reduction terminates, reactor is adjusted to reaction condition and carries out Fischer-Tropsch synthesis.Reaction condition is: temperature 275 ° of C, and pressure is 2.0MPa, and unstripped gas is H
2/ CO=2.0(mol ratio), air speed is 6000h
-1, recycle ratio is 2.0.
Above-mentioned Fischer-Tropsch synthesis Evaluation results is as shown in table 1.
Embodiment 2,
Be loaded in fixed bed reactors by 10g Fischer-Tropsch synthetic iron-based catalyst, catalyst consists of 100Fe/5La/3Cu/1Rb/30Al
2o
3(for mass ratio).H is passed into fixed bed reactors
2, adjustment reactor pressure is 3.0MPa, and air speed is 500h
-1, recycle ratio is 15, and reactor rises to constant temperature 24h after 260 ° of C by room temperature with the programming rate of 5 ° of C/h.Reducing atmosphere is switched to H
2/ C
3h
8the mist of (mol ratio is 10:1), air speed 500h
-1, recycle ratio is 10, keeps temperature to be that 260 ° of C reduction 48h obtain the ferrum-based catalyst after reducing, be designated as B under this atmosphere.
After reduction terminates, reactor is adjusted to reaction condition and carries out Fischer-Tropsch synthesis.Reaction condition is: temperature 270 ° of C, and pressure is 3.0MPa, and unstripped gas is H
2/ CO=1.2(mol ratio), air speed is 5000h
-1, recycle ratio is 2.0.
Embodiment 3,
Be loaded in fixed bed reactors by 10g Fischer-Tropsch synthetic iron-based catalyst, catalyst consists of 100Fe/3Cr/1K/15SiO
2(for mass ratio).H in fixed bed reactors
2/ C
3h
8the mist of=1, adjustment reactor pressure is 0.3MPa, and air speed is 1000h
-1, recycle ratio be 0(both tail gas do not circulate), reactor rises to constant temperature 30h after 280 ° of C by room temperature with the programming rate of 10 ° of C/h.Obtain the ferrum-based catalyst after reducing, be designated as C.
After reduction terminates, reactor is adjusted to reaction condition and carries out Fischer-Tropsch synthesis.Reaction condition is: temperature 280 ° of C, and pressure is 3.0MPa, and unstripped gas is H
2/ CO=2.0(mol ratio), air speed is 5000h
-1, recycle ratio is 2.0.
Embodiment 4,
Be loaded in fixed bed reactors by 10g Fischer-Tropsch synthetic iron-based catalyst, catalyst consists of 100Fe/3Cu/1Cs/20Al
2o
3(for mass ratio).C is passed into reactor
2h
4, adjustment reactor pressure is 2.0MPa, and air speed is 500h
-1, recycle ratio is 10, and reactor rises to constant temperature 36h after 280 ° of C by room temperature with the programming rate of 10 ° of C/h.Obtain the ferrum-based catalyst after reducing, be designated as D.
After reduction terminates, reactor is adjusted to reaction condition and carries out Fischer-Tropsch synthesis.Reaction condition is: temperature 260 ° of C, and pressure is 2.0MPa, and unstripped gas is H
2/ CO=1.6(mol ratio), air speed is 7000h
-1, recycle ratio is 3.0.
Embodiment 5,
Be loaded in fixed bed reactors by 8g Fischer-Tropsch synthetic iron-based catalyst, catalyst consists of 100Fe/1Mo/8Cu/3K/20SiO
2(for mass ratio).C is passed into reactor
4h
8, adjustment reactor pressure is 0.2MPa, and air speed is 500h
-1, recycle ratio is 10, and reactor rises to constant temperature 24h after 285 ° of C by room temperature with the programming rate of 10 ° of C/h.Obtain the ferrum-based catalyst after reducing, be designated as E.
After reduction terminates, reactor is adjusted to reaction condition and carries out Fischer-Tropsch synthesis.Reaction condition is: temperature 265 ° of C, and pressure is 1.5MPa, and unstripped gas is H
2/ CO=1.6(mol ratio), air speed is 5000h
-1, recycle ratio is 3.0.
Above-mentioned Fischer-Tropsch synthesis Evaluation results is as shown in table 1.
Can be learnt by data in table 1, catalyst provided by the invention is under the reaction temperature of fixed bed reactors 240 ~ 300 ° of C, and activity is higher, and deactivation rate is comparatively slow, C
5 +selective height.In addition, in course of reaction, fixed bed reactors do not occur, because the bed pressure drop that catalyst breakage causes increases, to illustrate that the antiwear property of catalyst in course of reaction reduced by the present invention is stronger.
Below describe embodiment of the present invention in detail, a lot of improvement can be done for a person skilled in the art obviously and change and essence spirit of the present invention can not be deviated from.All these changes and improvements are all within protection scope of the present invention.
Table 1 evaluating catalyst result
Claims (3)
1. a method of reducing for fixed bed Fischer-Tropsch synthetic iron-based catalyst, comprises the steps:
Ferrum-based catalyst is added in fixed bed reactors; The mist passing into gaseous hydrocarbon or hydrogen and gaseous hydrocarbon in described fixed bed reactors carries out reduction reaction, namely realizes the reduction to described ferrum-based catalyst; In the mist of described hydrogen and described gaseous hydrocarbon, the mol ratio of described hydrogen and described gaseous hydrocarbon is 1 ~ 100:1;
Described ferrum-based catalyst is made up of Fe, structural promoter, carrier and electronic auxiliary;
The mass ratio of described Fe, described structural promoter, described carrier and described electronic auxiliary is 100:0.5 ~ 20:5 ~ 40:0.2 ~ 10;
Described structural promoter is at least one in Cu, La, Ce, Cr, Zn, Mn and Mo;
Described carrier is SiO
2, Al
2o
3and ZrO
2middle at least one;
Described electronic auxiliary is at least one in Li, Na, K, Ru and Cs;
Described gaseous hydrocarbon is CH
4, C
2h
4, C
2h
6, C
3h
6, C
3h
8and C
4h
8middle at least one;
The pressure of described reduction reaction is 0.1 ~ 4.0MPa, and temperature is 240 ~ 350 DEG C, and the time is 10 ~ 60h;
In described reduction reaction, the air speed of the mist of described gaseous hydrocarbon or described hydrogen and described carburet hydrogen is 500 ~ 5000h
-1; Recycle ratio, namely the mol ratio of circulating air and virgin gas is 0 ~ 20.
2. method of reducing according to claim 1, is characterized in that: before the mist passing into described gaseous hydrocarbon or described hydrogen and described gaseous hydrocarbon, and described method also comprises pass into the step that hydrogen carries out prereduction in described reactor.
3. method of reducing according to claim 2, is characterized in that: the air speed passing into described hydrogen is 500 ~ 5000h
-1, recycle ratio is 0 ~ 15;
The temperature of described prereduction is 240 ~ 400 DEG C, and the time is 1 ~ 48h, and pressure is 0.1 ~ 4.0MPa.
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| US9643164B2 (en) * | 2013-06-28 | 2017-05-09 | Dow Global Technologies Llc | Iron-based catalysts and treatment process therefor for use in Fischer-Tropsch reactions |
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| CN103934044B (en) * | 2014-03-03 | 2016-08-17 | 内蒙古伊泰煤制油有限责任公司 | Fischer-Tropsch synthesis device is utilized once to reduce the method for more than 15t catalyst |
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| CN105709742B (en) * | 2014-12-04 | 2019-04-09 | 神华集团有限责任公司 | A kind of iron-base fischer-tropsch catalyst and its preparation method and application and a kind of Fischer-Tropsch synthesis method |
| CN105478128B (en) * | 2015-11-23 | 2018-05-25 | 中科合成油技术有限公司 | Fischer-Tropsch synthesis iron-based catalyst with high abrasion resistance and high reaction activity and preparation method thereof |
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| CN108728151B (en) * | 2017-04-19 | 2021-05-14 | 中国石油化工股份有限公司 | Alpha-olefin production method and alpha-olefin production system |
| CN108722421B (en) * | 2017-04-19 | 2022-02-08 | 中国石油化工股份有限公司 | Catalyst, preparation method and application thereof, reduction activation method of catalyst precursor and preparation method of heterogeneous diesel oil |
| CN111036278B (en) * | 2018-10-15 | 2023-03-10 | 中国石油化工股份有限公司 | Method for preparing low-carbon olefin from synthesis gas |
| CN111068745B (en) * | 2018-10-19 | 2023-02-17 | 中国石油化工股份有限公司 | Process for producing alpha-olefins |
| CN111068743B (en) * | 2018-10-19 | 2022-09-27 | 中国石油化工股份有限公司 | Production method of low-carbon olefin |
| CN111686824A (en) * | 2020-06-11 | 2020-09-22 | 中科合成油内蒙古有限公司 | In-situ regeneration method for ruthenium-based catalyst synthesized by Fischer-Tropsch fixed bed |
| CN111905747B (en) * | 2020-08-10 | 2023-07-28 | 中科合成油内蒙古有限公司 | Iron-based Fischer-Tropsch synthesis catalyst with non-carbide active phase, and preparation method and application thereof |
| EP4330344A2 (en) | 2021-04-28 | 2024-03-06 | Torrgas Technology B.V. | Process to prepare lower olefins |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004026796A2 (en) * | 2002-09-20 | 2004-04-01 | Conocophillips Company | Slurry activation of fischer-tropsch catalyst with carbon monoxide co-feed |
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| CN1247305C (en) * | 2004-03-19 | 2006-03-29 | 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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Address after: 101407 No.1, south 2nd Yueyuan street, C District, Yanqi Development Zone, Huairou District, Beijing Patentee after: Zhongke synthetic oil Technology Co.,Ltd. Address before: 101407 No.1, south 2nd Yueyuan street, C District, Yanqi Development Zone, Huairou District, Beijing Patentee before: SYNFUELS CHINA TECHNOLOGY Co.,Ltd. |