CN104785263A - Loaded type iron-based catalyst, and preparation method and application thereof - Google Patents
Loaded type iron-based catalyst, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a loaded type iron-based catalyst, and a preparation method and an application thereof. The catalyst takes nano rodlike alpha aluminum oxide as a carrier for loading metal particles, and the metal particles are iron nanoparticles. The invention also discloses the application of the nano rodlike alpha aluminum oxide.
Description
Technical field
The present invention relates to catalyst, particularly relate to a kind of load-type iron-based Catalysts and its preparation method and the purposes in preparation of low carbon olefines by synthetic gas system.
Background technology
Low-carbon alkene (C
2 =~ C
4 =) be important Elementary Chemical Industry raw material, be widely used in the production of large synthetic materials such as plastics, synthetic resin, fiber, rubber.At present, low-carbon alkene mainly through petrochemical industry distance, as light oil cracking is produced.Along with the exhaustion day by day of petroleum resources, an International Petroleum Price high position is hovered, and causes the production cost of low-carbon alkene to improve constantly, significantly limit low-carbon alkene industrial expansion.Therefore, while improvement conventional preparation techniques, exploitation non-petroleum feedstocks is prepared low-carbon alkene technology and is had great importance.
Compared with petroleum resources, coal, natural gas and biomass resource relative abundance.At present, by the synthesis gas of coal, natural gas or biomass source, realize industrial applications through methyl alcohol two-step method alkene, but there is flow process complexity, the problems such as process route is long, and one-time investment is large.Synthesis gas is through the technology of the direct preparing low-carbon olefins of Fiscber-Tropscb synthesis, not only can reduce the undue dependence to petroleum resources, promote the industrial development in oil-poor area, and avoid the generation of the intermediate products such as methyl alcohol, have that flow process is short, energy consumption and the low advantage of coal consumption, china natural resources is utilized to balanced and reasonable, guarantees that national energy security has very important strategic importance.
Synthesis gas directly transforms in producing light olefins system, and ferrum-based catalyst has larger competitive advantage compared to other metallic catalysts, and (2) as with low cost in (1) water-gas shift activity is higher, can directly transform low H
2the synthesis gas in the source such as coal, living beings of/CO ratio; (3), under the hot conditions of producing at applicable low-carbon alkene, methane selectively is lower.Compared with the catalyst of non-loading type, the catalyst of support type can realize the dispersion of active component, immobilized, reduces the Particle Breakage that coking causes, has better prospects for commercial application.Research finds, although take active material as the dispersion that catalyst prepared by carrier can realize active component, effectively overcome the problem of unsupported catalyst mechanical stability difference, but interaction strong between carrier and active component can produce the activation of catalyst and hinder, and is unfavorable for the high activity realizing catalyst.With the inert carrier that carbon nano-fiber and alpha-aluminium oxide are representative, more weak with active component Interaction Force, while realizing active component dispersion, effectively can promote reaction activation, be conducive to the effect between auxiliary agent and active component, thus come into one's own (De Jong etc., Science, 2012) day by day.But the general specific area of common block structure business alpha-aluminium oxide is less, be unfavorable for the dispersion of active component, immobilized.
Therefore, research is found and a kind ofly can be realized the high efficiency dispersion of active component, immobilized loading type iron is catalyst based seems particularly important.
Summary of the invention
The present invention aims to provide a kind of novel iron-based nanocatalyst and its production and use.
The present invention also will provide the novelty teabag of nano bar-shape alpha-aluminium oxide.
In a first aspect of the present invention, provide a kind of loading type iron catalyst based, described catalyst is with nano bar-shape alpha-aluminium oxide for carrier to load metal particle, and described metallic particles is iron nano-particle; On described catalyst, dispersed, the load of iron nano-particle is at alumina carrier surface.
In another preference, the load capacity of the catalyst based iron of described loading type iron is 1-40wt%; More preferably, be 5-25wt%; Best, be 5-10wt%.
In a second aspect of the present invention, provide the preparation method that a kind of loading type iron provided by the invention as above is catalyst based, described method comprises step:
(1) presoma of iron and solvent are mixed to get the precursor solution of iron; With
(2) be impregnated on nano bar-shape alpha-aluminium oxide by the precursor solution of iron, through ageing, drying, then high-temperature roasting, to obtain loading type iron catalyst based in reduction.
In another preference, carry out roasting at 150-600 DEG C; More preferably, be 250-500 DEG C; Best, be 400-500 DEG C.
In a third aspect of the present invention, the purposes that a kind of loading type iron provided by the invention as above of transmitance is catalyst based, as the catalyst of preparation of low carbon olefines by synthetic gas or for the synthesis of gas producing light olefins.
In a fourth aspect of the present invention, provide a kind of method of preparation of low carbon olefines by synthetic gas, described method uses loading type iron provided by the invention as above catalyst based.
In a fifth aspect of the present invention, provide the application of a kind of nano bar-shape alpha-aluminium oxide in preparation loading type iron provided by the invention as above is catalyst based.
In another preference, described nano bar-shape alpha-aluminium oxide is that nano level club forms by diameter, and crystalline phase is α type.
In another preference, described nano bar-shape alpha-aluminium oxide is prepared by following step:
(1) by alpha-aluminium oxide presoma drying and dehydrating, dry presoma is obtained; With
(2) presoma that calcining is dry, heating rate is at 1-10 DEG C/min, and calcining heat is at 400-1400 DEG C, and the calcination processing time is 1-12 hour, obtains nano bar-shape alpha-aluminium oxide.
In another preference, the presoma used can under certain roasting condition, be transformed into nano bar-shape alpha-aluminium oxide, specifically comprise gama-alumina, η-aluminium oxide, χ-aluminium oxide, other transitional aluminas, boehmite, boehmite, gibbsite, bayerite etc.
Accordingly, the invention provides a kind of preparation method of the iron-based nanocatalyst for the synthesis of gas producing light olefins.This preparation method achieves the high efficiency dispersion, immobilized of active component, and improve the activity of catalyst, stability, is a kind of very promising method preparing effective catalyst.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of nano bar-shape alpha-aluminium oxide and common alpha-aluminium oxide.
The XRD figure of Fig. 2 nano bar-shape alpha-aluminium oxide and common alpha-aluminium oxide.
Fig. 3 is Fe load at the transmission electron microscope picture of nano bar-shape alpha-aluminium oxide 1 and distribution diagram of element.
Fig. 4 is Fe load at the transmission electron microscope picture of common alpha-aluminium oxide and distribution diagram of element.
Fig. 5 is the transmission electron microscope picture of Fe load at nano bar-shape alpha-aluminium oxide 1 catalyst of roasting under excessive temperature.
Detailed description of the invention
Inventor, through extensive and deep research, has found a kind of iron-based nanocatalyst for the synthesis of gas producing light olefins.This catalyst is carrier loaded iron nano-particle with nano bar-shape alpha-aluminium oxide, utilizes the special club shaped structure of carrier and surface nature, obtain the new catalyst of iron nano-particle high degree of dispersion.This catalyst demonstrates the catalytic performance of higher preparation of low carbon olefines by synthetic gas.On this basis, the present invention is completed.
Nano bar-shape alpha-aluminium oxide
The nano bar-shape alpha-aluminium oxide that the present invention relates to, compared to common commercial alpha-aluminium oxide, it has special Rod-like shape, relatively high specific area; For pure α phase, there is nano bar-shape structure.
Nano bar-shape alpha-aluminium oxide provided by the invention is obtained by following step:
The first step, by alpha-aluminium oxide presoma drying and dehydrating;
Second step, calcines dried presoma under certain atmospheric condition, obtains nano bar-shape alpha-aluminium oxide.
The presoma of alpha-aluminium oxide described in said method can under certain roasting condition, be transformed into nano bar-shape alpha-aluminium oxide, specifically comprise gama-alumina, η-aluminium oxide, χ-aluminium oxide, other transitional aluminas, boehmite, boehmite, gibbsite, bayerite etc.
Calcination processing effect described in said method and the original crystal formation of presoma, calcining heat, heating rate and calcination time have certain relation, the original crystal formation of different presomas has different the suitableeest roasting conditions (comprising temperature, heating rate and time), calcining heat can be 400-1400 DEG C depending on the original crystal formation of presoma, heating rate controls at 1-10 DEG C/min, more excellent is 1-5 DEG C/min, the calcination processing time is 1-12 hour, and more excellent is 2-6 hour.Have certain interaction relation between sintering temperature and time, the time of roasting needed for temperature height is just short, and vice versa.
Iron-based nanocatalyst
Use nano bar-shape alpha-aluminium oxide, the invention provides a kind of iron-based nanocatalyst that can be used for for the preparation of preparation of low carbon olefines by synthetic gas, iron nano-particle high degree of dispersion on obtained iron-based nanocatalyst, immobilized, the load capacity of obtained iron-based nanocatalyst iron is 1-40wt%, preferred 5-25wt%, is more preferably 5-10wt%.
Iron-based nanocatalyst for the synthesis of gas producing light olefins provided by the invention prepares by following step: the solution presoma of iron and solvent being mixed to get described presoma.By this solution impregnation on nano bar-shape alpha-aluminium oxide, through ageing, drying, then high-temperature roasting, reduction obtain iron-based nanocatalyst.
In one embodiment of the invention, the preparation method for the synthesis of the iron-based nanocatalyst of gas producing light olefins comprises step:
The first step, is mixed to get the solution of described presoma by the presoma of iron and solvent;
Second step, is impregnated into the precursor solution of iron on nano bar-shape alpha-aluminium oxide, and through ageing, drying, then high-temperature roasting, reduction obtain iron-based nanocatalyst.
The presoma of the iron related in said method comprises ferric nitrate, ferric acetate, ferric citrate etc., and found by test inventor, the presoma of different iron affects not quite catalyst cupport effect and catalytic performance.
Sintering temperature is comparatively large to the performance impact of gained iron-based nanocatalyst, and find to carry out roasting at 150-600 DEG C by test inventor, preferred sintering temperature is 400-500 DEG C, roasting time 2-10 hour, and more excellent is 2-3 hour.Certain sintering temperature and have certain interaction relation between the time, the time of roasting needed for temperature height is just short, and vice versa.
The filtration of above-mentioned preparation method, washing, drying and ageing can be carried out according to the usual manner of this area.The presoma of iron can be prepared by equi-volume impregnating, such as but not limited to the disclosed method of document (G.Ertl etc. compile " Handbook of Heterogeneous Catalysis ", Wiley, 2008).
Preparation of low carbon olefines by synthetic gas
The invention provides a kind of method of preparation of low carbon olefines by synthetic gas, in fixed bed reactors, the normally used H in this area can be adopted
2atmosphere, and normally used heating rate reduces, and subsequently the temperature of reactor is down to conventional temperature, wherein uses iron-based nanocatalyst provided by the invention.Pass into synthesis gas (H
2/ CO=1) and pressure is risen to common numerical value gradually, outlet gas-phase product composition is by gas-chromatography on-line analysis.
The above-mentioned feature that the present invention mentions, or the feature that embodiment is mentioned can be combined.All features that this case description discloses can with any composition forms and use, each feature disclosed in description, anyly can provide identical, alternative characteristics that is impartial or similar object replaces.Therefore apart from special instruction, the feature disclosed is only general example that is impartial or similar features.
Major advantage of the present invention is:
1, catalyst provided by the invention is for carrier with nano bar-shape alpha-aluminium oxide, possesses the shape characteristic of nano bar-shape structure, the general carrier function of common aluminium oxide and the special carrier effect of nano aluminium oxide can be played simultaneously, because of but a kind of novel structural catalyst.
2, the present invention utilizes nano bar-shape alpha-aluminium oxide to be that carrier loaded iron nano-particle prepares high dispersive, immobilized iron nanocatalyst.Utilize the special appearance of carrier and higher specific area, optimize presoma composition, sintering temperature obtains high degree of dispersion, immobilized iron nano-particle, thus considerably improve the activity, selective of preparation of low carbon olefines by synthetic gas.
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, the usually conveniently conditioned disjunction condition of advising according to manufacturer.Unless otherwise indicated, otherwise all percentage, ratio, ratio or number by weight.
Unit in percent weight in volume in the present invention is well-known to those skilled in the art, such as, refer to the weight of solute in the solution of 100 milliliters.
Unless otherwise defined, all specialties used in literary composition and scientific words and one skilled in the art the meaning be familiar with identical.In addition, any method similar or impartial to described content and material all can be applicable in the inventive method.
Following embodiment can use alumina precursor to comprise boehmite, boehmite etc.; Iron presoma comprises ferric nitrate, ferric acetate, ferric citrate etc., and the Size Distribution of different iron presomas to Fe base nano-catalyst is little.In an embodiment of the present invention with boehmite, boehmite for alumina precursor; Be mainly the presoma of iron with ferric citrate, tell about advantage of the present invention.
In following embodiment, generally get 0.1g catalyst and add in the reaction tube of fixed bed reactors, at normal pressure, 15mL/min N
2350 DEG C are heated to the heating rate of 5 DEG C/min, at 15mL/min H under atmosphere
2reductase 12 h under atmosphere, following reaction actuator temperature is down to 340 DEG C.Pass into synthesis gas (H
2/ CO=1) and pressure is risen to 1MPa gradually.Outlet gas-phase product composition is by gas-chromatography on-line analysis.
Embodiment 1
Fe load is in the preparation (with tufted boehmite for alpha-aluminium oxide presoma) of nano bar-shape alpha-aluminium oxide catalyst
Get a certain amount of tufted boehmite presoma, at 120 DEG C of dry 12h.Dried sample is heated to 1300 DEG C with the heating rate of 5 DEG C/min under air atmosphere, roasting 4h, obtains alpha-aluminium oxide 1 and (be designated as α-Al
2o
3-1).Wherein aluminium oxide has club shaped structure (see Fig. 1), and crystalline phase characterizes through XRD and proves α type (see Fig. 2), and specific area is 13m
2/ g.
Measure the water absorption rate of nano bar-shape alpha-aluminium oxide 1.Weigh 1g nano bar-shape alpha-aluminium oxide 1 to mix with appropriate ironic citrate ammonium salt solution (with iron load capacity for 10wt% calculates), under normal temperature, ageing 12h is placed on 120 DEG C of dry 12h.Dried sample is heated to 500 DEG C with the heating rate of 5 DEG C/min under air atmosphere, roasting 2h, obtains catalyst precursor S1 (see Fig. 3).Getting 0.1g catalyst precursor adds in the reaction tube of fixed bed reactors, checks air-tightness.At normal pressure, 15mL/min N
2after being heated to 340 DEG C with the heating rate of 5 DEG C/min under atmosphere, pass into 15mL/min H
2reductase 12 h, passes into synthesis gas (H subsequently
2/ CO=1) and pressure is risen to 1MPa gradually.Outlet gas-phase product composition, by gas-chromatography on-line analysis, wherein connects the FID of capillary column for detecting hydrocarbon composition, connects the TCD of packed column for detecting CO, CO
2, H
2content.The reactivity of catalyst is represented by CO conversion ratio, selective by CO be converted into hydro carbons percentage (%C) and all in hydro carbons the percentage (%C) of low-carbon alkene represent.Reaction result shows that the high-dispersion nano catalyst of nano bar-shape alpha-aluminium oxide 1 load can significantly improve catalytic performance (table 1).This catalyst is because having high degree of dispersion, immobilized active particle and show the ratio of higher CO conversion ratio, higher hydrocarbon selective and selectivity of light olefin, higher alkene alkane, and outstanding catalyst stability.
Embodiment 2
Fe load is in the preparation (sheet boehmite is alpha-aluminium oxide presoma) of nano bar-shape alpha-aluminium oxide catalyst
Get a certain amount of sheet boehmite presoma, at 120 DEG C of dry 12h.Dried sample is heated to 1300 DEG C with the heating rate of 5 DEG C/min under air atmosphere, roasting 4h, obtains alpha-aluminium oxide 2 and (be designated as α-Al
2o
3-2).Wherein aluminium oxide has club shaped structure (see Fig. 1), and crystalline phase characterizes through XRD and proves α type (see Fig. 2), and specific area is 8m
2/ g.
Measure the water absorption rate of nano bar-shape alpha-aluminium oxide 2.Weigh 1g nano bar-shape alpha-aluminium oxide 2 to mix with appropriate ironic citrate ammonium salt solution (with iron load capacity for 10wt% calculates), under normal temperature, ageing 12h is placed on 120 DEG C of dry 12h.Dried sample is heated to 500 DEG C with the heating rate of 5 DEG C/min under air atmosphere, roasting 2h, obtains catalyst precursor S2.Getting 0.1g catalyst precursor adds in the reaction tube of fixed bed reactors, checks air-tightness.At normal pressure, 15mL/min N
2after being heated to 340 DEG C with the heating rate of 5 DEG C/min under atmosphere, pass into 15mL/min H
2reductase 12 h, passes into synthesis gas (H subsequently
2/ CO=1) and pressure is risen to 1MPa gradually.Outlet gas-phase product composition, by gas-chromatography on-line analysis, wherein connects the FID of capillary column for detecting hydrocarbon composition, connects the TCD of packed column for detecting CO, CO
2, H
2content.The reactivity of catalyst is represented by CO conversion ratio, selective by CO be converted into hydro carbons percentage (%C) and all in hydro carbons the percentage (%C) of low-carbon alkene represent.Reaction result shows that the high-dispersion nano catalyst of nano bar-shape alpha-aluminium oxide 2 load can significantly improve catalytic performance (table 1).This catalyst is because having high degree of dispersion, immobilized active particle and show the ratio of higher CO conversion ratio, higher hydrocarbon selective and selectivity of light olefin, higher alkene alkane, and outstanding catalyst stability.
Embodiment 3
The load of different Fe content is in the preparation of nano bar-shape alpha-aluminium oxide catalyst
Measure the water absorption rate of nano bar-shape alpha-aluminium oxide 1.Weigh 1g nano bar-shape alpha-aluminium oxide 1 and appropriate ironic citrate ammonium salt solution (be respectively 1 with iron load capacity, 5,20,30,40wt% calculates) mix, under normal temperature, ageing 12h is placed on 120 DEG C of dry 12h.Dried sample is heated to 500 DEG C with the heating rate of 5 DEG C/min under air atmosphere, roasting 2h, obtains catalyst precursor S3, S4, S5, S6, S7.Averaging of income particle diameter is added up in table 2 by TEM.Getting 0.1g catalyst precursor adds in the reaction tube of fixed bed reactors, checks air-tightness.At normal pressure, 15mL/min N
2after being heated to 340 DEG C with the heating rate of 5 DEG C/min under atmosphere, pass into 15mL/min H
2reductase 12 h, passes into synthesis gas (H subsequently
2/ CO=1) and pressure is risen to 1MPa gradually.Outlet gas-phase product composition, by gas-chromatography on-line analysis, wherein connects the FID of capillary column for detecting hydrocarbon composition, connects the TCD of packed column for detecting CO, CO
2, H
2content.The reactivity of catalyst is represented by CO conversion ratio, selective by CO be converted into hydro carbons percentage (%C) and all in hydro carbons the percentage (%C) of low-carbon alkene represent.
Embodiment 4
The Fe load of roasting under different temperatures is in the preparation of nano bar-shape alpha-aluminium oxide catalyst
Measure the water absorption rate of nano bar-shape alpha-aluminium oxide 1.Weigh 1g nano bar-shape alpha-aluminium oxide 1 to mix with appropriate ironic citrate ammonium salt solution (with iron load capacity for 10wt% calculates), under normal temperature, ageing 12h is placed on 120 DEG C of dry 12h.Dried sample is heated to 200,300,400,550 DEG C with the heating rate of 5 DEG C/min respectively under air atmosphere, roasting 2h, obtains catalyst precursor S8, S9, S10, S11.Averaging of income particle diameter is added up in table 2 by TEM.Getting 0.1g catalyst precursor adds in the reaction tube of fixed bed reactors, checks air-tightness.At normal pressure, 15mL/min N
2after being heated to 340 DEG C with the heating rate of 5 DEG C/min under atmosphere, pass into 15mL/min H
2reductase 12 h, passes into synthesis gas (H subsequently
2/ CO=1) and pressure is risen to 1MPa gradually.Outlet gas-phase product composition, by gas-chromatography on-line analysis, wherein connects the FID of capillary column for detecting hydrocarbon composition, connects the TCD of packed column for detecting CO, CO
2, H
2content.The reactivity of catalyst is represented by CO conversion ratio, selective by CO be converted into hydro carbons percentage (%C) and all in hydro carbons the percentage (%C) of low-carbon alkene represent.
Embodiment 5
Fe load is in the preparation (with ferric nitrate and ferric acetate for presoma) of nano bar-shape alpha-aluminium oxide 1 catalyst
Measure the water absorption rate of nano bar-shape alpha-aluminium oxide 1.Weigh 1g nano bar-shape alpha-aluminium oxide 1 to mix with appropriate iron nitrate solution or ferric acetate solution (with iron load capacity for 10wt% calculates), under normal temperature, ageing 12h is placed on 120 DEG C of dry 12h.Dried sample is heated to 500 DEG C with the heating rate of 5 DEG C/min under air atmosphere, roasting 2h, obtains catalyst precursor S12, S13.With the domain size distribution (see table 4) added up from TEM image, the difference that the catalyst prepared by different presoma is not large on particle diameter.Getting 0.1g catalyst precursor adds in the reaction tube of fixed bed reactors, checks air-tightness.At normal pressure, 15mL/min N
2after being heated to 340 DEG C with the heating rate of 5 DEG C/min under atmosphere, pass into 15mL/min H
2reductase 12 h, passes into synthesis gas (H subsequently
2/ CO=1) and pressure is risen to 1MPa gradually.Outlet gas-phase product composition, by gas-chromatography on-line analysis, wherein connects the FID of capillary column for detecting hydrocarbon composition, connects the TCD of packed column for detecting CO, CO
2, H
2content.The reactivity of catalyst is represented by CO conversion ratio, selective by CO be converted into hydro carbons percentage (%C) and all in hydro carbons the percentage (%C) of low-carbon alkene represent.Appraisal result is as shown in table 5, and result shows on catalytic performance, do not have too large difference with the catalyst of different iron precursor power.
Comparative example 1
Fe load is in the preparation of common alpha-aluminium oxide catalyst
Common alpha-aluminium oxide (is designated as α-Al
2o
3-3) specific area is 2m
2/ g, crystalline phase is α type (see Fig. 2), and purchased from Shandong Nuo Da Chemical Co., Ltd., its electron scanning micrograph as shown in Figure 1.Measure the water absorption rate of this common alpha-aluminium oxide.Weigh the common alpha-aluminium oxide of 1g to mix with appropriate ironic citrate ammonium salt solution (with iron load capacity for 10wt% calculates), under normal temperature, ageing 12h is placed on 120 DEG C of dry 12h.Dried sample is heated to 500 DEG C with the heating rate of 5 DEG C/min under air atmosphere, roasting 2h, obtains catalyst precursor S14 (see Fig. 4).Getting 0.1g catalyst precursor adds in the reaction tube of fixed bed reactors, checks air-tightness.At normal pressure, 15mL/min N
2after being heated to 340 DEG C with the heating rate of 5 DEG C/min under atmosphere, pass into 15mL/minH
2reductase 12 h, passes into synthesis gas (H subsequently
2/ CO=1) and pressure is risen to 1MPa gradually.Outlet gas-phase product composition, by gas-chromatography on-line analysis, wherein connects the FID of capillary column for detecting hydrocarbon composition, connects the TCD of packed column for detecting CO, CO
2, H
2content.The reactivity of catalyst is represented by CO conversion ratio, selective by CO be converted into hydro carbons percentage (%C) and all in hydro carbons the percentage (%C) of low-carbon alkene represent.On the catalyst that result shows common alpha-aluminium oxide load, iron particle generally comes off, and carrier no longer has load effect, and this phenomenon is very disadvantageous for commercial Application.Appraisal result, S1 activity poor (table 1) compared by the catalyst of common alpha-aluminium oxide load.When modulation air speed makes this catalyst and S1 have identical CO transform level, this catalyst has the ratio of lower hydrocarbon selective, selectivity of light olefin and alkene alkane, catalytic performance poor (table 1).
Comparative example 2
The preparation of nano bar-shape alpha-aluminium oxide catalyst under different roasting condition
Get a certain amount of tufted boehmite presoma, at 120 DEG C of dry 12h.Dried sample is heated to 1000 DEG C with the heating rate of 5 DEG C/min under air atmosphere, roasting 4h, obtains alpha-aluminium oxide 4 and (be designated as α-Al
2o
3-4).Wherein alumina crystalline phase characterizes through XRD and proves α and θ type mixing (see Fig. 2), and have laminated structure (see Fig. 1), specific area is 38m
2/ g.Measure the water absorption rate of alpha-aluminium oxide 4.Weigh 1g alpha-aluminium oxide 4 to mix with appropriate ironic citrate ammonium salt solution (with iron load capacity for 10wt% calculates), under normal temperature, ageing 12h is placed on 120 DEG C of dry 12h.Dried sample is heated to 500 DEG C with the heating rate of 5 DEG C/min under air atmosphere, roasting 2h, obtains catalyst precursor S15.Getting 0.1g catalyst precursor adds in the reaction tube of fixed bed reactors, checks air-tightness.At normal pressure, 15mL/min N
2after being heated to 340 DEG C with the heating rate of 5 DEG C/min under atmosphere, pass into 15mL/min H
2reductase 12 h, passes into synthesis gas (H subsequently
2/ CO=1) and pressure is risen to 1MPa gradually.Outlet gas-phase product composition, by gas-chromatography on-line analysis, wherein connects the FID of capillary column for detecting hydrocarbon composition, connects the TCD of packed column for detecting CO, CO
2, H
2content.The reactivity of catalyst is represented by CO conversion ratio, selective by CO be converted into hydro carbons percentage (%C) and all in hydro carbons the percentage (%C) of low-carbon alkene represent.Reaction result shows that S15 is because the direct load of active component is on non-pure phase alpha-aluminium oxide, and carrier and active component intermolecular forces are comparatively strong, and catalyst activity compares S1 activity poor (table 6).Correspond to a certain specific alumina precursor as can be seen here, need an appropriate turn brilliant temperature that it just can be made thoroughly to be converted into α phase, form the inert carrier useful to FTO reactivity.
Comparative example 3
Under too high sintering temperature, Fe load is in the preparation of nano bar-shape alpha-aluminium oxide 1 catalyst
Measure the water absorption rate of nano bar-shape alpha-aluminium oxide 1.Weigh 1g nano bar-shape alpha-aluminium oxide 1 to mix with appropriate ironic citrate ammonium salt solution (with iron load capacity for 10wt% calculates), under normal temperature, ageing 12h is placed on 120 DEG C of dry 12h.Dried sample is heated to 700 DEG C with the heating rate of 5 DEG C/min under air atmosphere, roasting 2h, obtains catalyst precursor S16.The domain size distribution (see table 7) added up from TEM image, too high sintering temperature causes particle increase even to be reunited, and sample S16 has larger grain diameter.Getting 0.1g catalyst precursor adds in the reaction tube of fixed bed reactors, checks air-tightness.At normal pressure, 15mL/min N
2after being heated to 340 DEG C with the heating rate of 5 DEG C/min under atmosphere, pass into 15mL/min H
2reductase 12 h, passes into synthesis gas (H subsequently
2/ CO=1) and pressure is risen to 1MPa gradually.Outlet gas-phase product composition, by gas-chromatography on-line analysis, wherein connects the FID of capillary column for detecting hydrocarbon composition, connects the TCD of packed column for detecting CO, CO
2, H
2content.The reactivity of catalyst is represented by CO conversion ratio, selective by CO be converted into hydro carbons percentage (%C) and all in hydro carbons the percentage (%C) of low-carbon alkene represent.Result shows that the catalyst of excessive temperature roasting causes catalytic activity and hydrocarbon selective obviously to worsen because of particle serious agglomeration, and catalyst stability is low, easy in inactivation (table 8).
Comparative example 4
Under too high load capacity, Fe load is in the preparation of nano bar-shape alpha-aluminium oxide 1 catalyst
Measure the water absorption rate of nano bar-shape alpha-aluminium oxide 1.Weigh 1g nano bar-shape alpha-aluminium oxide 1 to mix with appropriate ironic citrate ammonium salt solution (with iron load capacity for 65wt% calculates), under normal temperature, ageing 12h is placed on 120 DEG C of dry 12h.Dried sample is heated to 500 DEG C with the heating rate of 5 DEG C/min under air atmosphere, roasting 2h, obtains catalyst precursor S17.From TEM image (see Fig. 5), sample S17 due to the load capacity of iron too high, there is bulk deposition in iron particle, and grain diameter becomes large.Getting 0.1g catalyst precursor adds in the reaction tube of fixed bed reactors, checks air-tightness.At normal pressure, 15mL/min N
2after being heated to 340 DEG C with the heating rate of 5 DEG C/min under atmosphere, pass into 15mL/min H
2reductase 12 h, passes into synthesis gas (H subsequently
2/ CO=1) and pressure is risen to 1MPa gradually.Outlet gas-phase product composition, by gas-chromatography on-line analysis, wherein connects the FID of capillary column for detecting hydrocarbon composition, connects the TCD of packed column for detecting CO, CO
2, H
2content.The reactivity of catalyst is represented by CO conversion ratio, selective by CO be converted into hydro carbons percentage (%C) and all in hydro carbons the percentage (%C) of low-carbon alkene represent.Result shows, because load capacity is comparatively large, causes particle packing on catalyst, particle serious agglomeration occurs in course of reaction and causes catalytic activity and hydrocarbon selective obviously to worsen, and catalyst stability is low, easy in inactivation (table 8).
Table 1 embodiment 1-2 and comparative example 1 the catalytic performance of catalyst
Reaction condition: H
2/ CO=1,340 DEG C, 1MPa, (a) GHSV=9000mLh
-1g
cat -1, (b) GHSV=3000mLh
-1g
cat -1
The average grain diameter of table 2 embodiment 1-4 gained catalyst
| Numbering | The load capacity (wt%) of iron | Sintering temperature (DEG C) | Average grain diameter (nm) |
| S1 | 10 | 500 | 14.8 |
| S2 | 10 | 500 | 15.2 |
| S3 | 1 | 500 | 12.4 |
| S4 | 5 | 500 | 13.6 |
| S5 | 20 | 500 | 14.7 |
| S6 | 30 | 500 | 15.9 |
| S7 | 40 | 500 | 16.9 |
| S8 | 10 | 200 | 11.4 |
| S9 | 10 | 300 | 13.3 |
| S10 | 10 | 400 | 14.2 |
| S11 | 10 | 550 | 15.3 |
The catalytic performance of table 3 embodiment 1-4 prepared catalyst
The average grain diameter of table 4 embodiment 1,5 gained catalyst
| Numbering | S1 | S12 | S13 |
| The presoma of iron | Ferric citrate | Ferric nitrate | Ferric acetate |
| Sintering temperature (DEG C) | 500 | 500 | 500 |
| Particle diameter (nm) | 14.8 | 15.1 | 15.0 |
The catalytic performance of table 5 embodiment 1,5 gained catalyst
The catalytic performance of table 6 embodiment 1 and comparative example 2 gained catalyst
The average grain diameter of table 7 embodiment 1 and comparative example 3-4 gained catalyst
| Numbering | S1 | S16 | S17 |
| The load capacity (wt%) of iron | 10 | 10 | 65 |
| Sintering temperature (DEG C) | 500 | 700 | 500 |
| Particle diameter (nm) | 14.8 | 19.4 | 22.5 |
The catalytic performance of table 8 embodiment 1 and comparative example 3-4 gained catalyst
Result shows, rod-like nano alpha-aluminium oxide provided by the invention is the method that carrier prepares high dispersive, immobilized iron nanocatalyst, easy, efficient, be easy to operation.Utilize the new catalyst that this method is obtained, show better preparing low-carbon olefin performance relative to the direct load of iron at common block business α catalyst, the high degree of dispersion of iron nano-particle is described, is immobilizedly conducive to raising catalytic performance.The pure phase alpha-aluminium oxide adopting different alpha-aluminium oxide presoma to obtain under appropriate roasting condition generally has excellent catalytic performance.In catalyst preparation process, the particle diameter situation impact of presoma on prepared catalyst of different iron is little.And adopt the catalyst prepared by load capacity of different Fe, the iron nanocatalyst of different-grain diameter can be obtained, select suitable particle diameter to contribute to the raising of catalytic performance.If catalyst sintering temperature is too high or load capacity is too high, the reunion of catalyst granules can be caused and come off, catalytic performance is obviously declined.
The foregoing is only preferred embodiment of the present invention, and be not used to limit substantial technological context of the present invention, substantial technological content of the present invention is broadly defined in the right of application, any technology entities that other people complete or method, if with application right define identical, also or a kind of change of equivalence, be all covered by being regarded as among this right.
Claims (10)
1. a loading type iron is catalyst based, it is characterized in that, described catalyst is with nano bar-shape alpha-aluminium oxide for carrier to load metal particle, and described metallic particles is iron nano-particle.
2. loading type iron as claimed in claim 1 is catalyst based, and it is characterized in that, the load capacity of described iron is 1-40wt%; Preferred 5-25wt%; More preferably 5-10wt%.
3. loading type iron as claimed in claim 1 or 2 is catalyst based, it is characterized in that, on described catalyst, dispersed, the load of iron nano-particle is at alumina carrier surface.
4. the preparation method that the loading type iron as described in any one of claim 1-3 is catalyst based, is characterized in that, described method comprises step:
(1) presoma of iron and solvent are mixed to get the precursor solution of iron;
(2) be impregnated on nano bar-shape alpha-aluminium oxide by the precursor solution of iron, through ageing, drying, then high-temperature roasting, to obtain loading type iron catalyst based in reduction.
5. preparation method as claimed in claim 4, is characterized in that, carry out roasting at 150-600 DEG C; Preferred 250-500 DEG C; More preferably 400-500 DEG C.
6. the purposes that the loading type iron as described in any one of claim 1-3 is catalyst based, is characterized in that, as the catalyst of preparation of low carbon olefines by synthetic gas or for the synthesis of gas producing light olefins.
7. a method for preparation of low carbon olefines by synthetic gas, is characterized in that, described method uses the loading type iron as described in any one of claim 1-3 catalyst based.
8. the application of nano bar-shape alpha-aluminium oxide in the loading type iron of preparation as described in any one of claim 1-3 is catalyst based.
9. apply as claimed in claim 8, it is characterized in that, described nano bar-shape alpha-aluminium oxide is that nano level club forms by diameter, and crystalline phase is α type.
10. apply as claimed in claim 8 or 9, it is characterized in that, described nano bar-shape alpha-aluminium oxide is prepared by following step:
(1) by alpha-aluminium oxide presoma drying and dehydrating, dry presoma is obtained;
(2) presoma that calcining is dry, heating rate is at 1-10 DEG C/min, and calcining heat is at 400-1400 DEG C, and the calcination processing time is 1-12 hour, obtains nano bar-shape alpha-aluminium oxide.
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