CN103301840A - Supported high-dispersity Fischer-Tropsch synthesis metal catalyst, preparation method and application - Google Patents
Supported high-dispersity Fischer-Tropsch synthesis metal catalyst, preparation method and application Download PDFInfo
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Abstract
The invention discloses a supported high-dispersity Fischer-Tropsch synthesis metal catalyst, a preparation method and an application, which belong to the technical field of catalysts. According to the preparation method, nanometre metal Fe particles or nanometre CoFe alloy particles are uniformly dispersed and supported on MgO; a magnesium-iron hydrotalcite precursor and a magnesium-cobalt-iron hydrotalcite precursor are prepared at first; and then the supported high-dispersity metal catalyst is formed after calcination reduction for the prepared hydrotalcite precursors in a hydrogen-nitrogen mixed gas atmosphere, and topological structure transformation; and the grain size of the active centre of the catalyst is controlled by modulating the ratio of metals in the hydrotalcite precursors and a heating program in the calcination reduction process. Via the high dispersity of the active centre of the catalyst, the activity of the reaction is improved; via the simple and easy modulation of the type of the active centre of the catalyst and the grain size, the selectivity of different types of the reaction products is improved.
Description
Technical field
The invention belongs to catalyst technical field, particularly synthetic Metal catalyst materials, preparation method and application of a kind of support type high dispersive Fischer-Tropsch.
Background technology
The history of co hydrogenation (Fischer-Tropsch synthetic) can trace back to iron that nineteen twenty-two Fei Sheer and Top's rope utilize alkalization high pressure (＞100bar) the catalysis co hydrogenation prepares alkene down, it just causes people's extensive concern at the beginning of finding.Fischer-Tropsch is synthetic can be converted into oxygenatedchemicals such as alkane, alkene and alcohol with synthesis gas (carbon monoxide and hydrogen), and these products can be used as clean fuel and use.Along with the exhaustion day by day of petroleum resources, the synthetic important channel that solves the petroleum-based energy crisis that becomes undoubtedly of Fischer-Tropsch.
Yet, how improving reactivity and product selectivity is synthetic two major issues that need to be resolved hurrily of Fischer-Tropsch: the activity of Fischer-Tropsch synthesis is mainly dissociated by the rate determining step carbon monoxide and hydrocarbon intermediate hydrogenation determines, the activation energy of changing down control step can be accelerated reaction rate, improves reactivity; On the other hand, according to mechanism of polymerization, the product of Fischer-Tropsch synthesis generally meets Anderson-Shu Erci-Fu Luorui and distributes, and product is of a great variety, comprises oxygenatedchemicals such as alkane, alkene, alcohol, acid and ketone.
Catalyst is the key that solves active and selective these two problems of Fischer-Tropsch synthesis.Generally speaking, the noble ruthenium catalyst also has very high co hydrogenation activity even without auxiliary agent, grows the selectively also higher of carbochain hydrocarbon, but because its reserves are limited, is difficult in industrial realization large-scale application.Iron and cobalt in the 8th family's metal have the co hydrogenation activity equally.The ferrum-based catalyst product is based on lower carbon number hydrocarbons, and can produce oxygenatedchemicals such as alkene and alcohol; Ferrum-based catalyst also has catalytic activity to water gas shift reation simultaneously, so hydrogen and carbon monoxide ratio in its reactant synthesis gas can be much smaller than 2, improve the hydrogen ratio by the part carbon monoxide in the synthesis gas is carried out the steam conversion, so ferrum-based catalyst can be widely used in the lower synthesis gas of hydrogen ratio of coal and living beings preparation.It is higher that cobalt-base catalyst is compared the ferrum-based catalyst activity, and it is conducive to the generation of long carbochain hydrocarbon, but product is widely distributed, can be from C
1To C
100, cobalt-base catalyst is relatively harsher to the hydrogen in the reactant and carbon monoxide proportion requirement simultaneously, and hydrogen and carbon monoxide mol ratio are generally 2.But no matter be iron-based or cobalt-base catalyst, its reactive activity and specific product selective when the catalysis co hydrogenation has bigger room for promotion.
Fischer-Tropsch is synthetic to have structure sensitive property, and the type of catalyst active center, decentralization and crystallite dimension can exert an influence to its catalytic performance.At above problem, it is precursor with the hydrotalcite that the present invention proposes a kind of, utilize metal species on the hydrotalcite laminate, the easy modulation of ratio, the metal ion atom level is disperseed on the laminate, and the characteristics that the metal ion of different valence state is evaded distribution prepare the method for the synthetic metallic catalyst of support type high dispersive Fischer-Tropsch of various grain sizes.
Summary of the invention
The object of the present invention is to provide a kind of support type high dispersion metal Catalysts and its preparation method, and prepared catalyst is applied to Fischer-Tropsch synthesis.
A kind of support type high dispersive Fischer-Tropsch synthesizes metallic catalyst, it is characterized in that, the last even spread loads of MgO has nano metal Fe particle or even spread loads that nano Co Fe alloy particle is arranged.
The grain size range of Fe particle is 10nm to 20nm, and the grain size range of CoFe alloy particle is 10nm to 40nm.
Support type high dispersion metal method for preparing catalyst of the present invention is as follows:
(1) preparation of hydrotalcite precursor
A. the preparation of magnesium molten iron talcum precursor
With magnesium nitrate (Mg (NO
3)
26H
2O), ferric nitrate (Fe (NO
3)
39H
2O) be dissolved in and be made into salting liquid in the deionized water; With sodium carbonate (Na
2CO
3), NaOH (NaOH) is dissolved in proportionaling alkali-forming solution in another part deionized water, sodium carbonate and naoh concentration are preferably [Na in the aqueous slkali
2CO
3]=2[Fe
3+], [NaOH]=1.6 ([Mg
2+]+[Fe
3+]); Two kinds of solution are added simultaneously nucleation obtains starching attitude shape precipitation in the full back-mixing rotation liquid film reactor of rotation, then sediment is moved into crystallization in the polytetrafluoroethylkettle kettle, crystallization temperature is 40 ℃ to 200 ℃, crystallization time is 6 hours to 72 hours, wherein crystallization temperature is preferably 100 ℃, and crystallization time is preferably 24 hours; Through washing, dry, grind magnesium molten iron talcum powder;
Or the preparation of b. magnesium ferro-cobalt hydrotalcite precursor
With Mg (NO
3)
26H
2O, cobalt nitrate (Co (NO
3)
26H
2O), Fe (NO
3)
39H
2O is dissolved in and is made into salting liquid in the deionized water; With Na
2CO
3, NaOH is dissolved in proportionaling alkali-forming solution in another part deionized water, wherein sodium carbonate and concentration sodium hydroxide are preferably [Na in the aqueous slkali
2CO
3]=2[Fe
3+], [NaOH]=1.6 ([Mg
2+]+[Co
2+]+[Fe
3+]); Two kinds of solution are added simultaneously nucleation obtains starching attitude shape precipitation in the full back-mixing rotation liquid film reactor of rotation, then sediment is moved into crystallization in the polytetrafluoroethylkettle kettle, crystallization temperature is 40 ℃ to 200 ℃, crystallization time is 6 hours to 72 hours, wherein crystallization temperature is preferably 100 ℃, and crystallization time is preferably 24 hours; Through washing, dry, grind magnesium ferro-cobalt hydrotalcite powder;
(2) support type high dispersion metal Preparation of catalysts
The magnesium molten iron talcum powder that obtains after step (1) ground or magnesium ferro-cobalt hydrotalcite powder are at hydrogen (H
2) and nitrogen (N
2) (H
2/ N
2Volume ratio from 1/99 to pure H
2, H
2/ N
2Volume ratio is preferably 5/95) calcining reduction under the reducing atmosphere formed, reduction temperature is 300 ℃ to 800 ℃, best reduction temperature is 450 ℃; Heating rate is 0.5 ℃/min to 10 ℃/min, is preferably 1 ℃/min or 5 ℃/min, and the recovery time is 0.5 hour to 12 hours; Be preferably 1 hour to 4 hours.After finishing, reduction obtains the synthetic metallic catalyst of support type high dispersive Fischer-Tropsch.
The volume of salting liquid equates with the volume of aqueous slkali among preferred steps a and the b, the corresponding 200mL deionized water of further preferred every 320mmol NaOH during the preparation aqueous slkali.
When preparing magnesium molten iron talcum presoma in the preferred steps (1), Mg (NO
3)
2With Fe (NO
3)
3Mg in the salting liquid that is made into
2+With Fe
3+Mol ratio be 3/1 to 5/1, further preferred Mg
2+With Fe
3+Mol ratio be 3/1,4/1 and 5/1.
When preparing magnesium ferro-cobalt hydrotalcite precursor in the preferred steps (1), Mg (NO
3)
2, Co (NO
3)
2, Fe (NO
3)
3Mg in the salting liquid that is made into
2+/ Co
2+/ Fe
3+Mol ratio be 2/1/1 to 4/1/1, further preferred Mg
2+/ Co
2+/ Fe
3+Mol ratio be 2/1/1,3/1/1 and 4/1/1.
Support type high dispersion metal catalyst of the present invention is that precursor preparation is come with the hydrotalcite, utilizes the easy modulation of metal species on the hydrotalcite laminate to control the type in activated centre, prepares the single metallic catalyst of support type and support type alloy catalyst; Utilize the characteristics that metal ion atom level on the laminate is disperseed and the metal ion of different valence state is evaded distribution to realize the high dispersive of catalyst active center; With prepared hydrotalcite precursor calcining reduction under reducing atmosphere, namely form support type high dispersion metal catalyst after its process topological structure conversion; Control the crystallite dimension of catalyst active center by metal ratio and calcining reduction program in the modulation hydrotalcite precursor, for the single metallic catalyst of support type, the grain size range in its activated centre is 10nm to 20nm, for support type alloying metal catalyst, its grain size range is 10nm to 40nm.
When this catalyst is applied to Fischer-Tropsch synthesis, can improve reactive activity and high-carbon hydrocarbon (C
5+) and the oxygenatedchemicals product selectivity.
Description of drawings
Fig. 1 is magnesium iron (MgFe), magnesium ferro-cobalt (MgCoFe) the hydrotalcite precursor XRD figure of different metal molar ratio, and a is that magnesium iron ratio is 5/1 (Mg among the figure
5Fe), b is Mg
4Fe, c are Mg
3Fe, d are that Mg/Co/Fe is 4/1/1(Mg
4CoFe), e is Mg
3CoFe, f are Mg
2The hydrotalcite precursor XRD figure of CoFe.
Fig. 2 is the magnesia load iron (Fe/MgO) with various grain sizes activated centre by MgFe, MgCoFe hydrotalcite precursor preparation, magnesia load ferro-cobalt (CoFe/MgO) catalyst XRD figure.A is that crystallite dimension is the Fe/MgO catalyst (Fe/MgO-11.09nm) of 11.09nm among the figure, b is Fe/MgO-11.86nm, c is Fe/MgO-16.31nm, d is Fe/MgO-19.76nm, e is that crystallite dimension is the CoFe/MgO catalyst (CoFe/MgO-14.22nm) of 14.22nm, f is CoFe/MgO-15.38nm, and g is CoFe/MgO-27.92nm, and h is the XRD figure of CoFe/MgO-34.27nm catalyst.
The specific embodiment
Embodiment 1
(1) Mg
2+/ Fe
3+Be 5/1(Mg
5Fe) hydrotalcite precursor preparation
Take by weighing 42.7333g(166.6667mmol) Mg (NO
3)
26H
2O, 13.4667g(33.3333mmol) Fe (NO
3)
39H
2O is dissolved in the 200mL deionized water and is made into salting liquid; Take by weighing 7.0660g(66.6667mmol) Na
2CO
3And 12.8000g(320mmol) NaOH is dissolved in proportionaling alkali-forming solution in another part 200mL deionized water.Salting liquid and aqueous slkali are added simultaneously nucleation obtains starching attitude shape precipitation in the full back-mixing rotation liquid film reactor of rotation at a high speed, then sediment is moved in the polytetrafluoroethylkettle kettle, at 100 ℃ of following crystallization 24h.Crystallization finish by washing, dry, grind Mg
5Fe hydrotalcite powder.
(2) Fe/MgO Preparation of catalysts
Get the Mg after a certain amount of grinding
5Fe hydrotalcite precursor is at H
2With N
2(H
2/ N
2Volume ratio is 5/95) calcining reduction under the reducing atmosphere formed, reduction temperature is 450 ℃, heating rate is 1 ℃/min or 5 ℃/min, the recovery time is 1 hour to 4 hours, after finishing to reduction the Fe/MgO catalyst.Work as Mg
5450 ℃ of reduction after 1 hour, the crystallite dimension in its activated centre is 11.09nm(Fe/MgO-11.09nm to Fe hydrotalcite precursor with the heating rate of 5 ℃/min, accompanying drawing Fig. 2, a); Work as Mg
5450 ℃ of reduction after 4 hours, the crystallite dimension in its activated centre is 11.86nm(Fe/MgO-11.86nm to Fe hydrotalcite precursor with the heating rate of 1 ℃/min, accompanying drawing Fig. 2, b).
Embodiment 2
(1) Mg
2+/ Fe
3+Be 3/1(Mg
3Fe) hydrotalcite precursor preparation
Take by weighing 38.4600g(150mmol) Mg (NO
3)
26H
2O, 20.2000g(50mmol) Fe (NO
3)
39H
2O is dissolved in the 200mL deionized water and is made into salting liquid; Take by weighing 10.5990g(100mmol) Na
2CO
3And 12.8000g(320mmol) NaOH is dissolved in proportionaling alkali-forming solution in another part 200mL deionized water.Salting liquid and aqueous slkali are added simultaneously nucleation obtains starching attitude shape precipitation in the full back-mixing rotation liquid film reactor of rotation at a high speed, then sediment is moved in the polytetrafluoroethylkettle kettle, at 100 ℃ of following crystallization 24h.Crystallization finish by washing, dry, grind Mg
3Fe hydrotalcite powder.
(2) Fe/MgO Preparation of catalysts
Get the Mg after a certain amount of grinding
3Fe hydrotalcite precursor is at H
2With N
2(H
2/ N
2Volume ratio is 5/95) calcining reduction under the reducing atmosphere formed, reduction temperature is 450 ℃, heating rate is 1 ℃/min or 5 ℃/min, the recovery time is 1 hour to 4 hours, after finishing to reduction the Fe/MgO catalyst.
Embodiment 3
(1) Mg
2+/ Co
2+/ Fe
3+Be 4/1/1(Mg
4CoFe) hydrotalcite precursor preparation
Take by weighing 34.1867g(133.3333mmol) Mg (NO
3)
26H
2O, 9.7010g(33.3333mmol) Co (NO
3)
26H
2O, 14.4667g(33.3333mmol) Fe (NO
3)
39H
2O is dissolved in the 200mL deionized water and is made into salting liquid; Take by weighing 7.0660g(66.6667mmol) Na
2CO
3And 12.8000g(320mmol) NaOH is dissolved in proportionaling alkali-forming solution in another part 200mL deionized water.Two kinds of solution are added simultaneously nucleation obtains starching attitude shape precipitation in the full back-mixing rotation liquid film reactor of at a high speed rotation, then sediment is moved in the polytetrafluoroethylkettle kettle 100 ℃ of following crystallization 24h.Crystallization finish by washing, dry, grind Mg
4CoFe hydrotalcite powder.
(2) CoFe/MgO Preparation of catalysts
Get the Mg after a certain amount of grinding
4CoFe hydrotalcite precursor is at H
2With N
2(H
2/ N
2Volume ratio is 5/95) calcining reduction under the reducing atmosphere formed, reduction temperature is 450 ℃, heating rate is 1 ℃/min or 5 ℃/min, the recovery time is 1 hour to 4 hours, after finishing to reduction the CoFe/MgO catalyst.Work as Mg
4450 ℃ of reduction after 1 hour, the crystallite dimension in its activated centre is 14.22nm(CoFe/MgO-14.22nm to CoFe hydrotalcite precursor with the heating rate of 5 ℃/min, accompanying drawing Fig. 2, e); Work as Mg
4450 ℃ of reduction after 4 hours, the crystallite dimension in its activated centre is 15.38nm(CoFe/MgO-15.38nm to CoFe hydrotalcite precursor with the heating rate of 1 ℃/min, accompanying drawing Fig. 2, f).
Embodiment 4
(1) Mg
2+/ Co
2+/ Fe
3+Be 2/1/1(Mg
2CoFe) hydrotalcite precursor preparation
Take by weighing 25.6400g(100mmol) Mg (NO
3)
26H
2O, 14.5515g(50mmol) Co (NO
3)
26H
2O, 20.2000g(50mmol) Fe (NO
3)
39H
2O is dissolved in the 200mL deionized water and is made into salting liquid; Take by weighing 10.5990g(100mmol) Na
2CO
3And 12.8000g(320mmol) NaOH is dissolved in proportionaling alkali-forming solution in another part 200mL deionized water.Two kinds of solution are added simultaneously nucleation obtains starching attitude shape precipitation in the full back-mixing rotation liquid film reactor of at a high speed rotation, then sediment is moved in the polytetrafluoroethylkettle kettle 100 ℃ of following crystallization 24h.Crystallization finish by washing, dry, grind Mg
2CoFe hydrotalcite powder.
(2) CoFe/MgO Preparation of catalysts
Get the Mg after a certain amount of grinding
2CoFe hydrotalcite precursor is at H
2With N
2(H
2/ N
2Volume ratio is 5/95) calcining reduction under the reducing atmosphere formed, reduction temperature is 450 ℃, heating rate is 1 ℃/min or 5 ℃/min, the recovery time is 1 hour to 4 hours, after finishing to reduction the CoFe/MgO catalyst.
Catalytic result
To carry out the CO hydrogenation reaction by Fe/MgO and the CoFe/MgO catalyst of the various grain sizes of MgFe, MgCoFe hydrotalcite precursor preparation by embodiment, reaction gas is H
2Gaseous mixture (H with CO
2/ CO volume ratio is preferably 2/1), volume space velocity is preferably 1500h
-1, reaction temperature is preferably 270 ℃, and reaction pressure is preferably 2MPa.
The catalytic performance of the Fe/MgO of above-described embodiment various grain sizes and CoFe/MgO catalyst is listed in table 1.
Table 1: the CO hydrogenation performance of the various grain sizes Fe/MgO of hydrotalcite precursor preparation and CoFe/MgO catalyst
Claims (8)
1. the synthetic metallic catalyst of support type high dispersive Fischer-Tropsch is characterized in that, the last even spread loads of MgO has nano metal Fe particle or even spread loads that nano Co Fe alloy particle is arranged.
2. according to the synthetic metallic catalyst of a kind of support type high dispersive Fischer-Tropsch of claim 1, it is characterized in that the grain size range of Fe particle is 10nm to 20nm, the grain size range of CoFe alloy particle is 10nm to 40nm.
3. the method for the synthetic metallic catalyst of a kind of support type high dispersive Fischer-Tropsch of preparation claim 1 is characterized in that, may further comprise the steps:
(1) preparation of hydrotalcite precursor
A. the preparation of magnesium molten iron talcum precursor
With magnesium nitrate (Mg (NO
3)
26H
2O), ferric nitrate (Fe (NO
3)
39H
2O) be dissolved in and be made into salting liquid in the deionized water; With sodium carbonate (Na
2CO
3), NaOH (NaOH) is dissolved in proportionaling alkali-forming solution in another part deionized water, wherein sodium carbonate and concentration sodium hydroxide are preferably [Na in the aqueous slkali
2CO
3]=2[Fe
3+], [NaOH]=1.6 ([Mg
2+]+[Fe
3+]); Two kinds of solution are added simultaneously nucleation obtains starching attitude shape precipitation in the full back-mixing rotation liquid film reactor of rotation, then sediment is moved into crystallization in the polytetrafluoroethylkettle kettle, crystallization temperature is 40 ℃ to 200 ℃, crystallization time is 6 hours to 72 hours, wherein crystallization temperature is preferably 100 ℃, and crystallization time is preferably 24 hours; Through washing, dry, grind magnesium molten iron talcum powder;
Or the preparation of b. magnesium ferro-cobalt hydrotalcite precursor
With Mg (NO
3)
26H
2O, cobalt nitrate (Co (NO
3)
26H
2O), Fe (NO
3)
39H
2O is dissolved in and is made into salting liquid in the deionized water; With Na
2CO
3, NaOH is dissolved in proportionaling alkali-forming solution in another part deionized water, sodium carbonate and concentration sodium hydroxide are preferably [Na in the aqueous slkali
2CO
3]=2[Fe
3+], [NaOH]=1.6 ([Mg
2+]+[Co
2+]+[Fe
3+]); Two kinds of solution are added simultaneously nucleation obtains starching attitude shape precipitation in the full back-mixing rotation liquid film reactor of rotation, then sediment is moved into crystallization in the polytetrafluoroethylkettle kettle, crystallization temperature is 40 ℃ to 200 ℃, crystallization time is 6 hours to 72 hours, wherein crystallization temperature is preferably 100 ℃, and crystallization time is preferably 24 hours; Through washing, dry, grind magnesium ferro-cobalt hydrotalcite powder;
(2) support type high dispersion metal Preparation of catalysts
The magnesium molten iron talcum powder that obtains after step (1) ground or magnesium ferro-cobalt hydrotalcite powder are at hydrogen (H
2) and nitrogen (N
2) (H
2/ N
2Volume ratio from 1/99 to pure H
2) calcining reduction under the reducing atmosphere formed, reduction temperature is 300 ℃ to 800 ℃, and heating rate is 0.5 ℃/min to 10 ℃/min, and the recovery time is 0.5 hour to 12 hours.
4. according to the method for claim 3, it is characterized in that the volume of the volume of salting liquid and aqueous slkali is preferably equal-volume among step a and the b.
5. according to the method for claim 3, it is characterized in that the corresponding 200mL deionized water of further preferred every 320mmol NaOH during the preparation aqueous slkali.
6. according to the method for claim 3, it is characterized in that, when preparing magnesium molten iron talcum in the preferred steps (1), Mg (NO
3)
2With Fe (NO
3)
3Mg in the salting liquid that is made into
2+With Fe
3+Mol ratio be preferably 3/1 to 5/1, Mg
2+With Fe
3+Mol ratio more preferably 3/1,4/1 and 5/1;
When preparing magnesium ferro-cobalt hydrotalcite in the preferred steps (1), Mg (NO
3)
2, Co (NO
3)
2, Fe (NO
3)
3Mg in the salting liquid that is made into
2+/ Co
2+/ Fe
3+Mol ratio be preferably 2/1/1 to 4/1/1, Mg
2+/ Co
2+/ Fe
3+Mol ratio more preferably 2/1/1,3/1/1 and 4/1/1.
7. according to the method for claim 3, it is characterized in that H in the reducing gases
2With N
2Volume ratio is preferably 5/95, and best reduction temperature is 450 ℃, and heating rate is preferably 1 ℃/min or 5 ℃/min, and the recovery time is preferably 1 hour to 4 hours.
8. the described metallic catalyst of claim 1 is synthetic for Fischer-Tropsch.
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