CN106311310A - Supported iron-based composite metal catalyst, and preparation method and application thereof - Google Patents
Supported iron-based composite metal catalyst, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of preparation of catalysts, and discloses a supported iron-based composite metal catalyst, a preparation method thereof, and an application of the supported iron-based composite metal catalyst in the field of direct preparation of low carbon olefins from synthetic gas. The catalyst contains 80-99 wt% of a pure-silica molecular sieve carrier and 1-20 wt% of an iron component supported on the pure-silica molecular sieve carrier, the iron component is a Fe-M compound, and M is one or more of Mn, K, Na, S, Cu and Zn. The average particle size of the obtained silicate1 is about 20 nm, and the catalyst has high specific surface area to realize uniform dispersion of active components and large contact area with reaction gas.
Description
Technical field
The invention belongs to field of catalyst preparation, in particular it relates to a kind of loading type iron based composite metal is urged
Agent and preparation method thereof, and use this load-type iron-based composite metal catalyst using synthesis gas straight
Connect the application prepared on low-carbon alkene field.
Background technology
In recent years, due to synthesis gas raw material sources widely, such as coal, natural gas, biomass energy etc.,
Make to become the study hotspot of educational circles and industrial quarters through synthesis gas alkene technology path.Especially coal alkene
Hydrocarbon is industry in the ascendant in current China, just flourish.Currently build or built
The olefin yield of the olefin hydrocarbon making by coal project become reaches more than 1,000 ten thousand tons.But, all these projects are all bases
In coal through synthesis gas, it is then passed through the technique that methanol carries out cracking again.And coal is straight through one-step method from syngas
Connect the process route preparing alkene, economical in theory beyond doubt, this technique without methanol intermediate,
Energy has the advantage of uniqueness.
It is distributed according to ASF, works as C2-C4When selectivity of light olefin is about 50%, the selectivity meeting of methane
It is about 30%.Although having been carried out substantial amounts of research for fischer-tropsch reaction catalyst, and define one and be
Row catalyst, but for reaction for preparing light olefins direct for synthesis gas, how to break ASF distribution,
Suppression carbochain increases, and reduces the generation of methane and carbon distribution remains the key issue needing to solve.
Wherein, ferrum-based catalyst is active due to cheap cost, higher selectivity of light olefin and catalysis,
Become synthesis gas and directly obtain the important catalyst of low-carbon alkene.The most load-type iron-based catalyst, by
In the specific surface area that catalytic carrier is higher, by dispersed for the nano-particle of ferrum, thus activity can be improved
Particle and the contact area of reacting gas.But, conventional gama-alumina and silica catalyst supports
With iron nano-particle, there is stronger interaction, and generate iron aluminide and the ferrum silication of more difficult reduction
Compound, and then reduce the activity of catalyst.Although additionally, some have the load of relatively weak interaction with ferrum
Body can be sufficiently reserved the catalysis activity of catalyst itself and can preferably contact with promoter
And act on, but can easily cause the nanometer of ferrum in course of reaction under the reaction condition of High Temperature High Pressure
The reunion of grain and carbon distribution, make catalysqt deactivation.So, how to find and to prepare suitable catalyst,
Make carrier, active component, promoter can reach optimum combination, in addition it is also necessary to further work and
Research.
Molecular sieve, due to itself regular geometry duct and higher specific surface area, is widely used in gas
Adsorb, separate and be used as in the middle of all kinds of catalytic reaction as catalyst or catalytic carrier.Kang etc.
People is with ZSM-5 molecular sieve as carrier, and ferric nitrate, copper nitrate and potassium carbonate are presoma, use dipping
Method is prepared for Fe-Cu-K/ZSM-5 catalyst, at 300 DEG C, 10bar and H2/ CO ratio is the bar of 2
Under part, it is thus achieved that selectivity of light olefin be 30%, methane selectively 20%, CO conversion ratio is 81%.
Das et al. is with silicalite-1 molecular sieve as carrier, and ferric nitrate, manganese nitrate is presoma, uses dipping
Method is prepared for Fe-Mn/Sil-1 (10%Fe, 5%Mn), 275 DEG C, 21bar, H2/ CO ratio is the bar of 1
Under part, it is thus achieved that selectivity of light olefin be 65%, CO conversion ratio is 5%, and research is thought, Mn can
Sintering and carbon distribution with suppression ferrum crystal.Equally, Xu et al. develops K-Fe-Mn/Si-2 catalyst
(8.3%-9.5%-9.6%), 20bar, 347 DEG C, H2Under conditions of/CO ratio is 2, obtain C2-C4
The highest selectivity is 70%, and CO conversion ratio is 70%-90% simultaneously.Research thinks that MnO can press down
Ethylene processed and propene, K2O is conducive to the chemisorbed of CO, thus improves CO conversion ratio and low
Carbon olefin selectivity.
Although having been carried out substantial amounts of research for fischer-tropsch reaction catalyst, and define a series of catalysis
Agent, but for reaction for preparing light olefins direct for synthesis gas, how to break ASF distribution, suppression
Carbochain increases, and reduces the generation of methane and carbon distribution remains the key issue needing to solve.
Therefore, in order to improve the catalytic performance of catalyst further, how to prepare particle diameter less, compare table
The silica zeolite that area is bigger, in addition it is also necessary to further work and research.
Summary of the invention
It is an object of the invention to overcome the catalyst of synthesis in prior art using synthesis gas directly to make
Defect in standby low-carbon alkene, and provide a kind of synthesis technique simple and easy to do, the support type that catalytic performance is good
Iron-based composite metal catalyst and its preparation method and application.
To achieve these goals, the invention provides a kind of load-type iron-based composite metal catalyst, its
In, this catalyst contains silica zeolite carrier and is supported on the ferrum group on described silica zeolite carrier
Point, described ferrum component is Fe-M complex, on the basis of the gross weight of described catalyst, and described total silicon
The content of molecular sieve carrier is 80-99 weight %, and the content of described ferrum component is 120 weight %；Wherein,
M is one or more in Mn, K, Na, S, Cu and Zn；Preferably, M be Mn and/or
K。
The invention provides the preparation method of above-mentioned load-type iron-based composite metal catalyst, wherein, the party
Method includes: by silica zeolite carrier impregnation in the solution containing source of iron, makes ferrum component be supported on described
On silica zeolite carrier, described source of iron contains Fe and M, wherein, M is Mn, K, Na, S,
One or more in Cu and Zn；
Preferably, described source of iron is the mixture of ferric nitrate, manganese nitrate and potassium nitrate.
Present invention also offers the catalyst prepared by said method.
Present invention also offers catalyst described above is using synthesis gas directly to prepare in low-carbon alkene
Application.
The present invention utilizes hydrothermal crystallisation methods to synthesize the particle diameter high-specific surface area total silicon molecule at about 20nm
Sieve silicate-1, and as carrier, there is higher specific surface area, active component can be made to disperse more
Uniformly, bigger with reacting gas contact area.Solution dipping method is used to prepare Fe-Mn-K/nano-Si-1
Catalyst, and this catalyst is used for synthesis gas directly prepare low-carbon alkene reaction.Synthesis technique is easy easily
OK, and show good catalytic performance, CO conversion ratio 50-90%, C2-C6 selectivity 50-70%.
The present invention is with the essential distinction of prior art, compares the silica zeolite micron of document report
Size, the silicate1 mean diameter that the present invention obtains is only about 20nm, has higher specific surface
Long-pending, active component dispersion can be made more uniform, bigger with reacting gas contact area.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with
Detailed description below is used for explaining the present invention together, but is not intended that limitation of the present invention.?
In accompanying drawing:
Fig. 1 is the SEM figure of the described spherical silica zeolite carrier of 1 preparation according to embodiments of the present invention；
Fig. 2 is the SEM of the load-type iron-based composite metal catalyst of 3 preparations according to embodiments of the present invention
Figure；
Fig. 3 is the specific surface area of the described spherical silica zeolite carrier of 1 preparation according to embodiments of the present invention
Collection of illustrative plates.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of load-type iron-based composite metal catalyst, wherein, this catalyst contains entirely
Si molecular sieves carrier and be supported on the ferrum component on described silica zeolite carrier, described ferrum component is
Fe-M complex, on the basis of the gross weight of described catalyst, the content of described silica zeolite carrier
For 80-99 weight %, the content of described ferrum component is 1-20 weight %；Wherein, M be Mn, K,
One or more in Na, S, Cu and Zn；
Preferably, M is Mn and/or K.
In accordance with the present invention it is preferred that, on the basis of the gross weight of described catalyst, described silica zeolite
The content of carrier is 85-95 weight %, and the content of described ferrum component is 5-15 weight %.
According to the present invention, described catalyst is hexagonal flake, and the particle diameter of described catalyst can be
0.1-0.3 micron, specific surface area can be 300-600 meters squared per gram, and most probable pore size can be 0.4-0.6
Nanometer, pore volume can be 0.1-0.2cm3/g；Preferably, the particle diameter of described catalyst is 0.1-0.2
Micron, specific surface area is 400-600 meters squared per gram, and most probable pore size is 0.45-0.55 nanometer, hole body
Amass as 0.15-0.2cm3/g；It is highly preferred that the particle diameter of described catalyst is 0.1-0.15 micron, than
Surface area is 500-600 meters squared per gram, and most probable pore size is 0.5 nanometer, and pore volume is 0.2cm3/g。
According to the present invention, described silica zeolite carrier is prepared by the method comprised the following steps:
(1) being 10-30 DEG C by template and esters of silicon acis in temperature, mechanical agitation speed is
Stir 1-3 hour under 800-1000r/min；
(2) it is transferred in water heating kettle carry out hydrothermal synthesis reaction by step (1) products therefrom；
(3) step (2) products therefrom is filtered, and filtration gained solid is washed with deionized,
It is dried；
(4) step (3) is dried products therefrom high-temperature roasting, removed template method；
Described template is TPAOH solution.
According to the present invention, the weight ratio of described esters of silicon acis and described template can become within the specific limits
Change, it is preferable that described esters of silicon acis can be 1:1-1.5 with the weight ratio of the consumption of described template, excellent
Selection of land, described esters of silicon acis can be 1:1-1.2 with the weight ratio of the consumption of described template, it is highly preferred that
Described esters of silicon acis can be 1:1 with the weight ratio of the consumption of described template.
Under preferable case, described esters of silicon acis can be tetraethyl orthosilicate.
According to the present invention, in step (1), template and esters of silicon acis can be 10-30 DEG C in temperature,
Mechanical agitation speed is to stir 1-3 hour under 800-1000r/min；Wherein, the equipment of described stirring does not has
There is concrete restriction, can be the conventional selection of those skilled in the art.
According to the present invention, in step (2), it is transferred in water heating kettle enter by step (1) products therefrom
Row hydrothermal synthesis reaction, wherein, the condition of described hydrothermal synthesis reaction includes: temperature can be
120-180 DEG C, the time can be 12-72 hour, it is preferable that temperature is 160-180 DEG C, and the time is 24-48
Hour, it is highly preferred that temperature is 180 DEG C, the time is 48 hours.
According to the present invention, in step (3), step (2) products therefrom is filtered, and institute will be filtered
Obtain solid to be washed with deionized, be dried；Wherein, described filtration and the condition of washing and equipment do not have
Body limits, and can be the conventional selection of those skilled in the art, not have for described dry condition and equipment
There is concrete restriction, can be the conventional selection of those skilled in the art, it is preferable that be in temperature
It is dried 10-14 hour at 100-140 DEG C, it is highly preferred that be dried 11-13 at temperature is 110-130 DEG C
Hour.
According to the present invention, in step (4), step (3) is dried products therefrom high-temperature roasting, de-
Template agent removing；Wherein, the equipment of described roasting is not particularly limited, and can be those skilled in the art's
Conventional selection, it is preferable that carry out in air atmosphere in tube furnace, and the condition bag of described roasting
Include: heating rate can be 1 DEG C/min to 10 DEG C/min, and temperature can be 500-550 DEG C, and the time can
Think 4-10 hour, it is preferable that heating rate is 2 DEG C/min to 4 DEG C/min, and temperature is 500-550 DEG C,
Time is 6-8 hour, it is highly preferred that heating rate is 2 DEG C/min-3 DEG C/min, temperature is 550 DEG C,
Time is 6-8 hour.
According to the present invention, described silica zeolite carrier is hexagonal flake, and the particle diameter of catalyst can
Thinking 0.1-0.3 micron, specific surface area can be 300-600 meters squared per gram, and most probable pore size can be
0.4-0.6 nanometer, pore volume can be 0.1-0.2cm3/g；Preferably, the particle diameter of described catalyst
For 0.1-0.2 micron, specific surface area is 400-600 meters squared per gram, and most probable pore size can be 0.45-0.55
Nanometer, pore volume is 0.15-0.2cm3/g；It is highly preferred that the particle diameter of described catalyst is 0.1-0.15
Micron, specific surface area is 500-600 meters squared per gram, and most probable pore size can be 0.5 nanometer, pore volume
For 0.2cm3/g。
Present invention also offers the preparation method of above-mentioned load-type iron-based composite metal catalyst, wherein, be somebody's turn to do
Method includes: by silica zeolite carrier impregnation in the solution containing source of iron, makes ferrum component be supported on institute
Stating on silica zeolite carrier, described source of iron contains Fe and M, wherein, M is Mn, K, Na, S,
One or more in Cu and Zn；
Preferably, described source of iron is the mixture of ferric nitrate, manganese nitrate and potassium nitrate.
According to the present invention, the condition of described dipping includes: temperature can be 10-80 DEG C, and the time can be
0.1-1 hour, it is preferable that temperature is 30-70 DEG C, the time was 0.5 hour, it is highly preferred that temperature is
50-60 DEG C, the time is 0.5 hour.
Under preferable case, according to the present invention, described solution is described source of iron to be dissolved in deionized water,
And the deionized water relative to 100ml, the consumption of described ferric nitrate is 0.7-2.1 gram, preferably 1-1.8
Gram, more preferably 1.2-1.6 gram；The consumption of described manganese nitrate is 0.41-1.23 gram；Described potassium nitrate
Consumption is 0.18-0.54 gram.
Present invention also offers the catalyst prepared by said method.
Present invention also offers above-mentioned load-type iron-based composite metal catalyst is using synthesis gas directly to make
Application in standby low-carbon alkene.
Hereinafter will be described the present invention by embodiment.
Embodiment 1
The present embodiment is for illustrating the preparation side of the load-type iron-based composite metal catalyst according to the present invention
Method.
Using silester is silicon source, and TPAOH is template, the ratio with mass ratio as 1:1
Example adds in conical flask or beaker, and at temperature is 25 DEG C, under stir speed (S.S.) is 800r/min, magnetic force stirs
Mix 2h；
Above-mentioned solution is transferred in rustless steel water heating kettle, incubation water heating reaction at temperature is 160 DEG C
48h；
By the product after hydrothermal synthesis reaction through deionized water wash, filter, and gained solid will be filtered
It is washed with deionized, and is 120 DEG C of drying 12 hours in temperature；
Further, dried products therefrom is placed in tube furnace, in air atmosphere, with 2 DEG C/min
Heating rate, be warming up to 550 DEG C of high-temperature roasting 6h, be prepared into spherical silica zeolite carrier, as
Shown in Fig. 1, wherein, described silica zeolite carrier is hexagonal flake, and the particle of described catalyst is straight
Footpath is 0.15 micron, and specific surface area is 500 meters squared per gram, and most probable pore size is 0.5 nanometer, pore volume
For 0.15cm3/g；
With 1.4 grams of ferric nitrates, 0.83 gram of manganese nitrate inorganic metal salt as presoma, it is dissolved in 100ml's
In deionized water, then by the spherical silica zeolite carrier impregnation of above-mentioned preparation ferric nitrate, manganese nitrate and
In the deionized water solution of potassium nitrate, result prepares Fe10%/Mn8%-silicate1 composite catalyst,
Temperature is dry for standby at 120 DEG C；
Result is prepared into load-type iron-based composite metal catalyst, and wherein, this catalyst contains total silicon molecule
Sieving carrier and be supported on ferrum component on described spherical silica zeolite carrier, described ferrum component is
Fe-Mn-K complex, on the basis of the gross weight of described catalyst, containing of described silica zeolite carrier
Amount is 82 weight %, and the content of described Fe is 10 weight %, and the content of described Mn is 8 weight %；
And
The particle diameter of described catalyst is 0.15 micron, and specific surface area is 400 meters squared per gram, may be used
Several apertures are 0.5 nanometer, and pore volume is 0.1cm3/g。
Embodiment 2
The present embodiment is for illustrating the preparation side of the load-type iron-based composite metal catalyst according to the present invention
Method.
Using silester is silicon source, and TPAOH is template, the ratio with mass ratio as 1:1
Example adds in conical flask or beaker, and at temperature is 25 DEG C, under stir speed (S.S.) is 800r/min, magnetic force stirs
Mix 2h；
Above-mentioned solution is transferred in rustless steel water heating kettle, incubation water heating reaction at temperature is 180 DEG C
48h；
By the product after hydrothermal synthesis reaction through deionized water wash, filter, and gained solid will be filtered
It is washed with deionized, and is 120 DEG C of drying 12 hours in temperature；
Dried products therefrom is placed in tube furnace, in air atmosphere, with the intensification of 2 DEG C/min
Speed, is warming up to 550 DEG C of high-temperature roasting 6h, is prepared into spherical silica zeolite carrier, wherein,
Described silica zeolite carrier is hexagonal flake, and the particle diameter of described silica zeolite carrier is
0.2 micron, specific surface area is 450 meters squared per gram, and most probable pore size is 0.5 nanometer, and pore volume is
0.13cm3/g；
With inorganic metal salts such as 1.4 grams of ferric nitrates, 0.83 gram of manganese nitrate and 0.36 gram of potassium nitrate as presoma,
It is dissolved in the deionized water of 10ml, then by the spherical silica zeolite carrier impregnation of above-mentioned preparation at nitre
In the deionized water solution of acid ferrum, manganese nitrate and potassium nitrate, prepared by result
Fe10%/Mn8%/K7%-silicate1 composite catalyst, dry for standby at temperature is 120 DEG C；
Result is prepared into load-type iron-based composite metal catalyst, and wherein, this catalyst contains total silicon molecule
Sieving carrier and be supported on the ferrum component on described spherical silica zeolite carrier, described ferrum component is
Fe-Mn-K complex, on the basis of the gross weight of described catalyst, containing of described silica zeolite carrier
Amount is 75 weight %, and the content of described Fe-Mn-K is 25 weight %；And
The particle diameter of described catalyst is 0.2 micron, and specific surface area is 400 meters squared per gram, most probable
Aperture is 0.5 nanometer, and pore volume is 0.12cm3/g。
Embodiment 3
The present embodiment is for illustrating the preparation side of the load-type iron-based composite metal catalyst according to the present invention
Method.
Using silester is silicon source, and TPAOH is template, the ratio with mass ratio as 1:1
Example adds in conical flask or beaker, and at temperature is 20 DEG C, under stir speed (S.S.) is 1000r/min, magnetic force stirs
After mixing 2h；
Above-mentioned solution is transferred in rustless steel water heating kettle, incubation water heating reaction at temperature is 180 DEG C
48h；
By the product after hydrothermal synthesis reaction through deionized water wash, filter, and gained solid will be filtered
It is washed with deionized, and is 120 DEG C of drying 12 hours in temperature；
Dried products therefrom is placed in tube furnace, in air atmosphere, with the intensification of 2 DEG C/min
Speed, is warming up to 550 DEG C of high-temperature roasting 6h, is prepared into spherical silica zeolite carrier, such as Fig. 3 institute
Showing, wherein, described silica zeolite carrier is hexagonal flake, and the particle of described silica zeolite carrier
A diameter of 0.16 micron, specific surface area is 550 meters squared per gram, and most probable pore size is 0.5 nanometer, hole body
Amass as 0.16cm3/g；
With 1.4 grams of ferric nitrates as presoma, it is dissolved in the deionized water of 10ml, then by above-mentioned preparation
Silica zeolite carrier impregnation in the deionized water solution of ferric nitrate, manganese nitrate and potassium nitrate, result
Preparation Fe10%-silicate1 composite catalyst, dry for standby at temperature is 120 DEG C；
Result is prepared into load-type iron-based composite metal catalyst, and wherein, this catalyst contains total silicon molecule
Sieving carrier and be supported on the ferrum component on described spherical silica zeolite carrier, described ferrum component is
Fe-Mn-K complex, on the basis of the gross weight of described catalyst, containing of described silica zeolite carrier
Amount is 90 weight %, and the content of described Fe is 10 weight %；And
The particle diameter of described catalyst is 0.16 micron, and specific surface area is 500 meters squared per gram, may be used
Several apertures are 0.5 nanometer, and pore volume is 0.11cm3/g。
Embodiment 4
The present embodiment is for illustrating the preparation side of the load-type iron-based composite metal catalyst according to the present invention
Method.
Preparing load-type iron-based composite metal catalyst according to the method for embodiment 3, institute's difference is,
Dried products therefrom is placed in tube furnace, in air atmosphere, with the heating rate of 5 DEG C/min,
Be warming up to 550 DEG C of high-temperature roasting 10h, be prepared into spherical silica zeolite carrier, wherein, described entirely
The particle diameter of si molecular sieves carrier is 0.1-0.2 micron, and specific surface area is 500 meters squared per gram, may be used
Several apertures are 0.5 nanometer, and pore volume is 0.1-0.2cm3/g；
Result is prepared into load-type iron-based composite metal catalyst, and wherein, this catalyst contains total silicon molecule
Sieving carrier and be supported on the ferrum component on described spherical silica zeolite carrier, described ferrum component is
Fe-Mn-K complex, on the basis of the gross weight of described catalyst, containing of described silica zeolite carrier
Amount is 70 weight %, and the content of described Fe-Mn-K is 30 weight %；And
The particle diameter of described catalyst is 0.15 micron, and specific surface area is 480 meters squared per gram, may be used
Several apertures are 0.5 nanometer, and pore volume is 0.12cm3/g。
Comparative example 1
Preparing load-type iron-based composite metal catalyst according to the method for embodiment 3, institute's difference is,
Dried products therefrom is placed in tube furnace, in air atmosphere, with the intensification speed of 10 DEG C/min
Rate, is warming up to 550 DEG C of high-temperature roasting 6h, is prepared into silica zeolite carrier, and wherein, described total silicon divides
The particle diameter of son sieve carrier is 0.2 micron, and specific surface area is 400 meters squared per gram, and most probable pore size is
0.5 nanometer, pore volume is 0.1cm3/g；
Result is prepared into load-type iron-based composite metal catalyst, and wherein, this catalyst contains total silicon molecule
Sieving carrier and be supported on the ferrum component on described spherical silica zeolite carrier, described ferrum component is
Fe-Mn-K complex, on the basis of the gross weight of described catalyst, containing of described silica zeolite carrier
Amount is 95 weight %, and the content of described Fe-Mn-K is 5 weight %；And
The particle diameter of described catalyst is 0.2 micron, and specific surface area is 350 meters squared per gram, most probable
Aperture is 0.5 nanometer, and pore volume is 0.09cm3/g。
Application Example 1
Selecting fixed bed reactors, catalyst embodiment 1 prepared is at H2Reductase 12 h under atmosphere, also
Former temperature 350 DEG C, is passed through synthesis gas, air speed 1000/h, (H2/ CO=1), pressure 10bar, heat up speed
Degree is 10 DEG C/min, reaction temperature 250 DEG C；
Product uses gas chromatographic analysis: CO conversion ratio is about 90%, C2-C6Selectivity of light olefin
70%.
Application Example 2
Selecting fixed bed reactors, catalyst embodiment 2 prepared is at H2Reductase 12 h under atmosphere, also
Former temperature 350 DEG C, is passed through synthesis gas, air speed 1000/h, (H2/ CO=3), pressure 40bar, heat up speed
Degree is 10 DEG C/min, reaction temperature 250 DEG C；
Product uses gas chromatographic analysis: CO conversion ratio is about 80%, C2-C6Selectivity of light olefin
65%.
Application Example 3
Selecting fixed bed reactors, catalyst embodiment 3 prepared is at H2Reductase 12 h under atmosphere, also
Former temperature 350 DEG C, is passed through synthesis gas, air speed 1000/h, (H2/ CO=2), pressure 30bar, heat up speed
Degree is 10 DEG C/min, reaction temperature 250 DEG C；
Product uses gas chromatographic analysis: CO conversion ratio is about 70%, C2-C6Selectivity of light olefin
60%.
Comparison study example 1
Being applied by catalyst according to the method for Application Example 2 is using synthesis gas directly to prepare low-carbon alkene
In, institute's difference is, what the catalyst in Application Example 2 replaced with prepared by comparative example 1 urges
Agent, result CO conversion ratio is about 50%, C2-C6Selectivity of light olefin 40%.
From above example 1-3 and comparative example 1 and Application Example 1-3 and the knot of Comparison study example 4
Really it can be seen that the synthesis technique of the load-type iron-based composite metal catalyst of present invention offer is easy easily
OK, structure-controllable, composition flexibly, is directly prepared low-carbon alkene catalysts and is provided newly for synthesis gas
Thinking, and CO conversion ratio can reach 60-90%, C2-C6Selectivity of light olefin can reach
50-70%.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, various possible compound modes are illustrated by the present invention the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (12)
1. a load-type iron-based composite metal catalyst, it is characterised in that this catalyst contains total silicon
Molecular sieve carrier and be supported on the ferrum component on described silica zeolite carrier, described ferrum component is
Fe-M complex, on the basis of the gross weight of described catalyst, the content of described silica zeolite carrier
For 80-99 weight %, the content of described ferrum component is 1-20 weight %；Wherein, M be Mn, K,
One or more in Na, S, Cu and Zn；
Preferably, M is Mn and/or K.
Catalyst the most according to claim 1, wherein, with the gross weight of described catalyst as base
Standard, the content of described silica zeolite carrier is 85-95 weight %, and the content of described ferrum component is 5-15
Weight %.
Catalyst the most according to claim 1 and 2, wherein, described catalyst is hexagonal flake,
And the particle diameter of described catalyst is 0.1-0.3 micron, specific surface area is 300-600 meters squared per gram,
Most probable pore size is 0.4-0.6 nanometer, and pore volume is 0.1-0.2cm3/g。
4. according to the catalyst described in any one in claim 1-3, wherein, described total silicon molecule
Sieve carrier is prepared by the method comprised the following steps:
(1) being 10-30 DEG C by template and esters of silicon acis in temperature, mechanical agitation speed is
Stir 1-3 hour under 800-1000r/min；
(2) it is transferred in water heating kettle carry out hydrothermal synthesis reaction by step (1) gained solution；
(3) step (2) products therefrom is filtered, and filtration gained solid is washed with deionized,
It is dried；
(4) step (3) is dried products therefrom high-temperature roasting, removed template method；
Described template is TPAOH solution.
Catalyst the most according to claim 4, wherein, described esters of silicon acis is tetraethyl orthosilicate,
The condition of described hydrothermal synthesis reaction includes: temperature is 120-180 DEG C, and the time is 12-72 hour；Institute
The condition stating high-temperature roasting removed template method includes: heating rate is 1 DEG C/min to 10 DEG C/min, temperature
Degree is for 500-550 DEG C, and the time is 4-10 hour.
6. according to the catalyst described in claim 4 or 5, wherein, described esters of silicon acis and described template
The weight ratio of the consumption of agent is 1:1-1.5.
Catalyst the most according to claim 4, wherein, described silica zeolite carrier is six sides
Lamellar, and the particle diameter of described silica zeolite carrier is 0.1-0.3 micron, specific surface area is 300-600
Meters squared per gram, most probable pore size is 0.4-0.6 nanometer, and pore volume is 0.1-0.2cm3/g。
8. the preparation of load-type iron-based composite metal catalyst described in any one in claim 1-7
Method, wherein, the method includes: by silica zeolite carrier impregnation in the solution containing source of iron, make
Ferrum component is supported on described silica zeolite carrier, and described source of iron contains Fe and M, and wherein, M is
One or more in Mn, K, Na, S, Cu and Zn；
Preferably, described source of iron is the mixture of ferric nitrate, manganese nitrate and potassium nitrate.
Method the most according to claim 8, wherein, the condition of described dipping includes: temperature is
10-80 DEG C, the time is 0.1-1 hour.
Method the most according to claim 8, wherein, described solution is for be dissolved in described source of iron
In deionized water, and the deionized water relative to 100ml, the consumption of described ferric nitrate is 0.7-2.1 gram,
The consumption of described manganese nitrate is 0.41-1.23 gram, and the consumption of described potassium nitrate is 0.18-0.54 gram.
The catalyst that in 11. claim 8-10, preparation method described in any one prepares.
In 12. claim 1-7 and 11, catalyst described in any one is using synthesis gas directly to prepare
Application in low-carbon alkene.
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