CN106311310B - A kind of load-type iron-based composite metal catalyst and its preparation method and application - Google Patents
A kind of load-type iron-based composite metal catalyst and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to field of catalyst preparation, a kind of load-type iron-based composite metal catalyst and preparation method thereof is disclosed, and the application on low-carbon alkene field is directly being prepared using synthesis gas using the load-type iron-based composite metal catalyst.Wherein, the iron component that the catalyst contains silica zeolite carrier and is supported on the silica zeolite carrier, the iron group is divided into Fe-M compound, on the basis of the total weight of the catalyst, the content of the silica zeolite carrier is 80-99 weight %, and the content of the iron component is 1-20 weight %；Wherein, one of M Mn, K, Na, S, Cu and Zn or a variety of.The silicate1 average grain diameter that the present invention obtains is only 20nm or so, has higher specific surface area, and active component dispersion can be made more uniform, bigger with reaction gas contact area.
Description
Technical field
The invention belongs to field of catalyst preparation, and in particular, to a kind of load-type iron-based composite metal catalyst and its
Preparation method, and directly prepared on low-carbon alkene field using the load-type iron-based composite metal catalyst using synthesis gas
Application.
Background technique
In recent years, due to the extensive raw material sources of synthesis gas, such as coal, natural gas, biomass energy etc., so that through synthesizing
Gas alkene technology path becomes the research hotspot of educational circles and industry.Especially coal-to-olefin is Fang Xingwei in current China
The industry of Chinese mugwort, is flourishing.The olefin yield for the coal to olefin project currently built or built up is up to more than 1000
Ten thousand tons.However, all these projects are all based on coal through synthesis gas, the technique then cracked again by methanol.And coal passes through
The process route that one-step method from syngas directly prepares alkene is crossed, is theoretically undoubtedly economy, the technique is without in methanol
Mesosome has unique advantage on energy.
It is distributed according to ASF, works as C2-C4When selectivity of light olefin is about 50%, the selectivity of methane can be about 30%.To the greatest extent
A large amount of research has been carried out for Fischer-Tropsch reaction catalyst in pipe, and forms a series of catalyst, but for synthesis gas
For direct reaction for preparing light olefins, how to break ASF distribution, inhibit carbochain to increase, and the generation for reducing methane and carbon distribution are still
It is so the critical issue for needing to solve.
Wherein, ferrum-based catalyst becomes synthesis due to cheap cost, higher selectivity of light olefin and catalytic activity
Gas directly obtains the important catalyst of low-carbon alkene.Especially load-type iron-based catalyst compares table since catalytic carrier is higher
Area, can be evenly dispersed by the nano particle of iron, to improve the contact area of active particle and reaction gas.However, often
Gama-alumina and silica catalyst supports and iron nano-particle have stronger interaction, and generate more difficult go back
Former iron aluminide and iron silicides, and then reduce the activity of catalyst.In addition, although some and iron is with weaker mutual
The carrier of effect can be sufficiently reserved the catalytic activity of catalyst itself and preferably can contact and make with co-catalyst
With, but can easily lead to the reunion of the nano particle of iron and carbon distribution during the reaction under the reaction condition of high temperature and pressure,
Make catalyst inactivation.So how to find and prepare suitable catalyst, make carrier, active component, co-catalyst can reach
To optimal combination, it is also necessary to further work and research.
Geometry duct and higher specific surface area of the molecular sieve due to rule itself, are widely used in the absorption of gas, divide
It is used as in all kinds of catalysis reactions from and as catalyst or catalytic carrier.Kang et al. using ZSM-5 molecular sieve as carrier,
Ferric nitrate, copper nitrate and potassium carbonate are presoma, are prepared for Fe-Cu-K/ZSM-5 catalyst using infusion process, at 300 DEG C,
10bar and H2Under conditions of/CO ratio is 2, the selectivity of light olefin of acquisition is 30%, and methane selectively 20%, CO turns
Rate is 81%.Das et al. is using silicalite-1 molecular sieve as carrier, ferric nitrate, and manganese nitrate is presoma, using infusion process
It is prepared for Fe-Mn/Sil-1 (10%Fe, 5%Mn), 275 DEG C, 21bar, H2Under conditions of/CO ratio is 1, the low-carbon alkene of acquisition
Hydrocarbon-selective is that 65%, CO conversion ratio is 5%, and research is thought, Mn can inhibit sintering and the carbon distribution of iron crystal.Equally, Xu etc.
People develops K-Fe-Mn/Si-2 catalyst (8.3%-9.5%-9.6%), 20bar, and 347 DEG C, H2The condition that/CO ratio is 2
Under, obtain C2-C4Highest selectivity is 70%, while CO conversion ratio is 70%-90%.Research thinks that MnO can inhibit second
Alkene and propene, K2O is conducive to the chemisorption of CO, to improve CO conversion ratio and selectivity of light olefin.
Although a large amount of research has been carried out for Fischer-Tropsch reaction catalyst, and a series of catalyst are formd,
For reaction for preparing light olefins direct for synthesis gas, how to break ASF distribution, inhibit carbochain to increase, and reduce the life of methane
It is still the critical issue for needing to solve at carbon distribution.
Therefore, in order to further increase the catalytic performance of catalyst, how to prepare that partial size is smaller, and specific surface area is bigger
Silica zeolite, it is also necessary to further work and research.
Summary of the invention
It is an object of the invention to overcome the catalyst synthesized in the prior art directly preparing low-carbon alkene using synthesis gas
The defects of hydrocarbon, and provide that a kind of synthesis technology is simple and easy to do, the good load-type iron-based composite metal catalyst of catalytic performance and
Preparation method and application.
To achieve the goals above, the present invention provides a kind of load-type iron-based composite metal catalysts, wherein the catalysis
The iron component that agent contains silica zeolite carrier and is supported on the silica zeolite carrier, it is multiple that the iron group is divided into Fe-M
Object is closed, on the basis of the total weight of the catalyst, the content of the silica zeolite carrier is 80-99 weight %, the iron
The content of component is 120 weight %；Wherein, one of M Mn, K, Na, S, Cu and Zn or a variety of；Preferably, M be Mn and/
Or K.
The present invention provides the preparation methods of above-mentioned load-type iron-based composite metal catalyst, wherein this method comprises: will
Silica zeolite carrier impregnation is supported on iron component on the silica zeolite carrier in the solution containing source of iron, described
Source of iron contains Fe and M, wherein one of M Mn, K, Na, S, Cu and Zn or a variety of；
Preferably, the source of iron is the mixture of ferric nitrate, manganese nitrate and potassium nitrate.
The present invention also provides the catalyst prepared by the above method.
The present invention also provides catalyst described above, and the application in low-carbon alkene is directly being prepared using synthesis gas.
The present invention synthesizes partial size in the high-specific surface area silica zeolite of 20nm or so using hydrothermal crystallisation methods
Silicate-1, and as carrier, there is higher specific surface area, active component dispersion can be made more uniform, with reaction gas
Contact level product is bigger.Fe-Mn-K/nano-Si-1 catalyst is prepared using solution dipping method, and the catalyst is used to close
Low-carbon alkene reaction is directly prepared at gas.Synthesis technology is simple and easy to do, and shows good catalytic performance, CO conversion ratio 50-
90%, C2-C6 selectivity 50-70%.
The essential distinction of the present invention and the prior art is, compares silica zeolite micron-scale reported in the literature, this
Inventing obtained silicate1 average grain diameter is only 20nm or so, has higher specific surface area, can make active component dispersion more
Add uniformly, it is bigger with reaction gas contact area.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the SEM figure of the spherical silica zeolite carrier of 1 preparation according to embodiments of the present invention；
Fig. 2 is the SEM figure of the load-type iron-based composite metal catalyst of 3 preparation according to embodiments of the present invention；
Fig. 3 is the specific surface area map of the spherical silica zeolite carrier of 1 preparation according to embodiments of the present invention.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of load-type iron-based composite metal catalysts, wherein the catalyst contains silica zeolite
Carrier and the iron component being supported on the silica zeolite carrier, the iron group is divided into Fe-M compound, with the catalysis
On the basis of the total weight of agent, the content of the silica zeolite carrier is 80-99 weight %, and the content of the iron component is 1-20
Weight %；Wherein, one of M Mn, K, Na, S, Cu and Zn or a variety of；
Preferably, M is Mn and/or K.
In accordance with the present invention it is preferred that on the basis of the total weight of the catalyst, the content of the silica zeolite carrier
For 85-95 weight %, the content of the iron component is 5-15 weight %.
According to the present invention, the catalyst is hexagonal flake, and the particle diameter of the catalyst can be micro- for 0.1-0.3
Rice, specific surface area can be 300-600 meters squared per gram, and most probable pore size can be 0.4-0.6 nanometers, and pore volume can be
0.1-0.2cm3/g；Preferably, the particle diameter of the catalyst is 0.1-0.2 microns, and specific surface area is 400-600 squares
Rice/gram, most probable pore size is 0.45-0.55 nanometers, pore volume 0.15-0.2cm3/g；It is highly preferred that the grain of the catalyst
Sub- diameter is 0.1-0.15 microns, and specific 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, the silica zeolite carrier is made by method comprising the following steps:
It (1) is 10-30 DEG C in temperature by template and esters of silicon acis, mechanical stirring rate is to stir under 800-1000r/min
1-3 hours；
(2) step (1) products therefrom is transferred in water heating kettle and carries out hydrothermal synthesis reaction；
(3) step (2) products therefrom is filtered, and filtering obtained solid is washed with deionized, is dried；
(4) by step (3) dry products therefrom high-temperature roasting, removed template method；
The template is tetrapropylammonium hydroxide solution.
According to the present invention, the weight ratio of the esters of silicon acis and the template can change in a certain range, it is preferable that
The weight ratio of the dosage of the esters of silicon acis and the template can be 1:1-1.5, it is preferable that the esters of silicon acis and the template
The weight ratio of the dosage of agent can be 1:1-1.2, it is highly preferred that the weight ratio of the dosage of the esters of silicon acis and the template can
Think 1:1.
Under preferable case, the esters of silicon acis can be ethyl orthosilicate.
It according to the present invention, can be 10-30 DEG C in temperature by template and esters of silicon acis in step (1), mechanical stirring speed
Rate is to stir 1-3 hours under 800-1000r/min；Wherein, the equipment of the stirring is not particularly limited, and can be this field skill
The conventional selection of art personnel.
According to the present invention, in step (2), it is anti-that step (1) products therefrom is transferred to progress hydrothermal synthesis in water heating kettle
It answers, wherein the condition of the hydrothermal synthesis reaction includes: that temperature can be 120-180 DEG C, and the time can be 12-72 hours, excellent
Selection of land, temperature are 160-180 DEG C, and the time is 24-48 hours, 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 obtained solid deionization will be filtered
Water washing, drying；Wherein, the condition and equipment of the filtering and washing are not particularly limited, and can be those skilled in the art
Conventional selection, the condition and equipment of the drying are not particularly limited, can be the conventional choosing of those skilled in the art
It selects, it is preferable that it is 10-14 hours dry at being 100-140 DEG C in temperature, it is highly preferred that dry at being 110-130 DEG C in temperature
11-13 hours.
According to the present invention, in step (4), by step (3) dry products therefrom high-temperature roasting, removed template method；Wherein,
The equipment of the roasting is not particularly limited, can be those skilled in the art conventional selection, it is preferable that in tube furnace
It is carried out under air atmosphere and the condition of the roasting includes: that heating rate can be for 1 DEG C/min to 10 DEG C/min, temperature
It can be 500-550 DEG C, the time can be 4-10 hours, it is preferable that heating rate is 2 DEG C/min to 4 DEG C/min, and temperature is
500-550 DEG C, the time is 6-8 hours, it is highly preferred that heating rate is 2 DEG C/min -3 DEG C/min, temperature is 550 DEG C, the time
It is 6-8 hours.
According to the present invention, the silica zeolite carrier is hexagonal flake, and the particle diameter of 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 nanometers, and pore volume can be with
For 0.1-0.2cm3/g；Preferably, the particle diameter of the catalyst is 0.1-0.2 microns, and specific surface area is 400-600 squares
Rice/gram, most probable pore size can be 0.45-0.55 nanometers, pore volume 0.15-0.2cm3/g；It is highly preferred that the catalyst
Particle diameter be 0.1-0.15 micron, specific surface area be 500-600 meters squared per gram, most probable pore size can be 0.5 nanometer,
Pore volume is 0.2cm3/g。
The present invention also provides the preparation methods of above-mentioned load-type iron-based composite metal catalyst, wherein this method comprises:
By silica zeolite carrier impregnation in the solution containing source of iron, it is supported on iron component on the silica zeolite carrier, institute
It states source of iron and contains Fe and M, wherein one of M Mn, K, Na, S, Cu and Zn or a variety of；
Preferably, the source of iron is the mixture of ferric nitrate, manganese nitrate and potassium nitrate.
According to the present invention, the condition of the dipping, which includes: temperature, to be 10-80 DEG C, and the time can be 0.1-1 hours,
Preferably, temperature is 30-70 DEG C, and the time is 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, the solution be by the source of iron dissolution in deionized water, and relative to
The deionized water of 100ml, the dosage of the ferric nitrate are 0.7-2.1 grams, preferably 1-1.8 grams, more preferably 1.2-1.6 grams；
The dosage of the manganese nitrate is 0.41-1.23 grams；The dosage of the potassium nitrate is 0.18-0.54 grams.
The present invention also provides the catalyst prepared by the above method.
The present invention also provides above-mentioned load-type iron-based composite metal catalysts, and low-carbon alkene is directly being prepared using synthesis gas
Application in hydrocarbon.
The present invention will be described in detail by way of examples below.
Embodiment 1
The present embodiment is used to illustrate the preparation method of load-type iron-based composite metal catalyst according to the present invention.
Use silester for silicon source, tetrapropylammonium hydroxide is template, and taper is added for the ratio of 1:1 with mass ratio
Bottle or beaker in, at being 25 DEG C in temperature in the case where stirring rate is 800r/min magnetic agitation 2h；
Above-mentioned solution is transferred in stainless steel water heating kettle, incubation water heating reacts 48h at being 160 DEG C in temperature；
Product after hydrothermal synthesis reaction is washed through deionized water, is filtered, and obtained solid deionization will be filtered
Water washing, and be 120 DEG C in temperature and dry 12 hours；
Further, products therefrom after drying is placed in tube furnace, in air atmosphere, with the heating speed of 2 DEG C/min
Rate is warming up to 550 DEG C of high-temperature roasting 6h, is prepared into spherical silica zeolite carrier, as shown in Figure 1, wherein the total silicon point
Son sieve carrier is hexagonal flake, and the particle diameter of the catalyst is 0.15 micron, and specific surface area is 500 meters squared per grams, most
Can several apertures be 0.5 nanometer, pore volume 0.15cm3/g；
Using 1.4 grams of ferric nitrates, 0.83 gram of manganese nitrate inorganic metal salt as presoma, it is dissolved in the deionized water of 100ml,
Again by the spherical silica zeolite carrier impregnation of above-mentioned preparation in the deionized water solution of ferric nitrate, manganese nitrate and potassium nitrate,
As a result Fe10%/Mn8%-silicate1 composite catalyst is prepared, is dried for standby at being 120 DEG C in temperature；
As a result be prepared into load-type iron-based composite metal catalyst, wherein the catalyst contain silica zeolite carrier with
And it is supported on iron component on the spherical silica zeolite carrier, the iron group is divided into Fe-Mn-K compound, with the catalyst
Total weight on the basis of, the content that the content of the silica zeolite carrier is 82 weight %, the Fe is 10 weight %, described
The content of Mn is 8 weight %；And
The particle diameter of the catalyst is 0.15 micron, and specific surface area is 400 meters squared per grams, most probable pore size 0.5
Nanometer, pore volume 0.1cm3/g。
Embodiment 2
The present embodiment is used to illustrate the preparation method of load-type iron-based composite metal catalyst according to the present invention.
Use silester for silicon source, tetrapropylammonium hydroxide is template, and taper is added for the ratio of 1:1 with mass ratio
Bottle or beaker in, at being 25 DEG C in temperature in the case where stirring rate is 800r/min magnetic agitation 2h；
Above-mentioned solution is transferred in stainless steel water heating kettle, incubation water heating reacts 48h at being 180 DEG C in temperature；
Product after hydrothermal synthesis reaction is washed through deionized water, is filtered, and obtained solid deionization will be filtered
Water washing, and be 120 DEG C in temperature and dry 12 hours；
Products therefrom after drying is placed in tube furnace, in air atmosphere, with the heating rate of 2 DEG C/min, heating
To 550 DEG C of high-temperature roasting 6h, it is prepared into spherical silica zeolite carrier, wherein
The silica zeolite carrier is hexagonal flake, and the particle diameter of the silica zeolite carrier is 0.2 micron,
Specific surface area is 450 meters squared per grams, and most probable pore size is 0.5 nanometer, pore volume 0.13cm3/g；
Using 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
In the deionized water of 10ml, then by the spherical silica zeolite carrier impregnation of above-mentioned preparation in ferric nitrate, manganese nitrate and potassium nitrate
Deionized water solution in, as a result prepare Fe10%/Mn8%/K7%-silicate1 composite catalyst, temperature be 120 DEG C
Under be dried for standby；
As a result be prepared into load-type iron-based composite metal catalyst, wherein the catalyst contain silica zeolite carrier with
And it is supported on the iron component on the spherical silica zeolite carrier, the iron group is divided into Fe-Mn-K compound, with the catalysis
On the basis of the total weight of agent, the content that the content of the silica zeolite carrier is 75 weight %, the Fe-Mn-K is 25 weights
Measure %；And
The particle diameter of the catalyst is 0.2 micron, and specific surface area is 400 meters squared per grams, most probable pore size 0.5
Nanometer, pore volume 0.12cm3/g。
Embodiment 3
The present embodiment is used to illustrate the preparation method of load-type iron-based composite metal catalyst according to the present invention.
Use silester for silicon source, tetrapropylammonium hydroxide is template, and taper is added for the ratio of 1:1 with mass ratio
In bottle or beaker, at being 20 DEG C in temperature in the case where stirring rate is 1000r/min after magnetic agitation 2h；
Above-mentioned solution is transferred in stainless steel water heating kettle, incubation water heating reacts 48h at being 180 DEG C in temperature；
Product after hydrothermal synthesis reaction is washed through deionized water, is filtered, and obtained solid deionization will be filtered
Water washing, and be 120 DEG C in temperature and dry 12 hours；
Products therefrom after drying is placed in tube furnace, in air atmosphere, with the heating rate of 2 DEG C/min, heating
To 550 DEG C of high-temperature roasting 6h, it is prepared into spherical silica zeolite carrier, as shown in Figure 3, wherein the silica zeolite carries
Body is hexagonal flake, and the particle diameter of the silica zeolite carrier is 0.16 micron, and specific surface area is 550 meters squared per grams,
Most probable pore size is 0.5 nanometer, pore volume 0.16cm3/g；
It using 1.4 grams of ferric nitrates as presoma, is dissolved in the deionized water of 10ml, then by the silica zeolite of above-mentioned preparation
As a result it is compound to prepare Fe10%-silicate1 in the deionized water solution of ferric nitrate, manganese nitrate and potassium nitrate for carrier impregnation
Catalyst is dried for standby at being 120 DEG C in temperature；
As a result be prepared into load-type iron-based composite metal catalyst, wherein the catalyst contain silica zeolite carrier with
And it is supported on the iron component on the spherical silica zeolite carrier, the iron group is divided into Fe-Mn-K compound, with the catalysis
On the basis of the total weight of agent, the content that the content of the silica zeolite carrier is 90 weight %, the Fe is 10 weight %；With
And
The particle diameter of the catalyst is 0.16 micron, and specific surface area is 500 meters squared per grams, most probable pore size 0.5
Nanometer, pore volume 0.11cm3/g。
Embodiment 4
The present embodiment is used to illustrate the preparation method of load-type iron-based composite metal catalyst according to the present invention.
Prepare load-type iron-based composite metal catalyst according to the method for embodiment 3, institute the difference is that, after drying
Products therefrom is placed in tube furnace, in air atmosphere, with the heating rate of 5 DEG C/min, is warming up to 550 DEG C of high-temperature roastings
10h is prepared into spherical silica zeolite carrier, wherein the particle diameter of the silica zeolite carrier is that 0.1-0.2 is micro-
Rice, specific surface area are 500 meters squared per grams, and most probable pore size is 0.5 nanometer, pore volume 0.1-0.2cm3/g；
As a result be prepared into load-type iron-based composite metal catalyst, wherein the catalyst contain silica zeolite carrier with
And it is supported on the iron component on the spherical silica zeolite carrier, the iron group is divided into Fe-Mn-K compound, with the catalysis
On the basis of the total weight of agent, the content that the content of the silica zeolite carrier is 70 weight %, the Fe-Mn-K is 30 weights
Measure %；And
The particle diameter of the catalyst is 0.15 micron, and specific surface area is 480 meters squared per grams, most probable pore size 0.5
Nanometer, pore volume 0.12cm3/g。
Comparative example 1
Prepare load-type iron-based composite metal catalyst according to the method for embodiment 3, institute the difference is that, after drying
Products therefrom is placed in tube furnace, in air atmosphere, with the heating rate of 10 DEG C/min, is warming up to 550 DEG C of high-temperature roastings
6h is prepared into silica zeolite carrier, wherein the particle diameter of the silica zeolite carrier is 0.2 micron, and specific surface area is
400 meters squared per grams, most probable pore size are 0.5 nanometer, pore volume 0.1cm3/g；
As a result be prepared into load-type iron-based composite metal catalyst, wherein the catalyst contain silica zeolite carrier with
And it is supported on the iron component on the spherical silica zeolite carrier, the iron group is divided into Fe-Mn-K compound, with the catalysis
On the basis of the total weight of agent, the content that the content of the silica zeolite carrier is 95 weight %, the Fe-Mn-K is 5 weights
Measure %；And
The particle diameter of the catalyst is 0.2 micron, and specific surface area is 350 meters squared per grams, most probable pore size 0.5
Nanometer, pore volume 0.09cm3/g。
Application Example 1
Fixed bed reactors are selected, catalyst prepared by embodiment 1 is in H2Reductase 12 h under atmosphere, 350 DEG C of reduction temperature,
It is passed through synthesis gas, air speed 1000/h, (H2/ CO=1), pressure 10bar, heating rate be 10 DEG C/min, 250 DEG C of reaction temperature；
Product uses gas chromatographic analysis: CO conversion ratio is about 90%, C2-C6Selectivity of light olefin 70%.
Application Example 2
Fixed bed reactors are selected, catalyst prepared by embodiment 2 is in H2Reductase 12 h under atmosphere, 350 DEG C of reduction temperature,
It is passed through synthesis gas, air speed 1000/h, (H2/ CO=3), pressure 40bar, heating rate be 10 DEG C/min, 250 DEG C of reaction temperature；
Product uses gas chromatographic analysis: CO conversion ratio is about 80%, C2-C6Selectivity of light olefin 65%.
Application Example 3
Fixed bed reactors are selected, catalyst prepared by embodiment 3 is in H2Reductase 12 h under atmosphere, 350 DEG C of reduction temperature,
It is passed through synthesis gas, air speed 1000/h, (H2/ CO=2), pressure 30bar, heating rate be 10 DEG C/min, 250 DEG C of reaction temperature；
Product uses gas chromatographic analysis: CO conversion ratio is about 70%, C2-C6Selectivity of light olefin 60%.
Comparison study example 1
Catalyst is applied according to the method for Application Example 2 and is directly being prepared in low-carbon alkene using synthesis gas, institute is not
It is with place, the catalyst in Application Example 2 is replaced with into catalyst prepared by comparative example 1, as a result CO conversion ratio is about
50%, C2-C6Selectivity of light olefin 40%.
It can be seen that from the result of above embodiments 1-3 and comparative example 1 and Application Example 1-3 and Comparison study example 4
The synthesis technology of load-type iron-based composite metal catalyst provided by the invention is simple and easy to do, structure-controllable, and composition is flexible, to close
Low-carbon alkene catalysts are directly prepared at gas and provide new thinking, and CO conversion ratio can reach 60-90%, C2-C6It is low
Carbene hydrocarbon-selective can reach 50-70%.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (13)
1. a kind of load-type iron-based composite metal catalyst, which is characterized in that the catalyst contain silica zeolite carrier and
The iron component being supported on the silica zeolite carrier, the iron group is divided into Fe-M compound, with the gross weight of the catalyst
On the basis of amount, the content of the silica zeolite carrier is 80-99 weight %, and the content of the iron component is 1-20 weight %；
Wherein, one of M Mn, K, Na, S, Cu and Zn or a variety of；
Wherein, the catalyst is hexagonal flake, and the particle diameter of the catalyst is 0.1-0.3 microns, and specific surface area is
300-600 meters squared per gram, most probable pore size are 0.4-0.6 nanometers, pore volume 0.1-0.2cm3/g。
2. catalyst according to claim 1, wherein M is Mn and/or K.
3. catalyst according to claim 1, wherein on the basis of the total weight of the catalyst, the total silicon molecule
The content for sieving carrier is 85-95 weight %, and the content of the iron component is 5-15 weight %.
4. catalyst described in any one of -3 according to claim 1, wherein the silica zeolite carrier is by including following
The method of step is made:
It (1) is 10-30 DEG C in temperature by template and esters of silicon acis, mechanical stirring rate is that stirring 1-3 is small under 800-1000r/min
When；
(2) step (1) acquired solution is transferred in water heating kettle and carries out hydrothermal synthesis reaction；
(3) step (2) products therefrom is filtered, and filtering obtained solid is washed with deionized, is dried；
(4) by step (3) dry products therefrom high-temperature roasting, removed template method；
The template is tetrapropylammonium hydroxide solution.
5. catalyst according to claim 4, wherein the esters of silicon acis is ethyl orthosilicate, the hydrothermal synthesis reaction
Condition include: temperature be 120-180 DEG C, the time be 12-72 hours；The condition of the high-temperature roasting removed template method includes:
Heating rate is 1 DEG C/min to 10 DEG C/min, and temperature is 500-550 DEG C, and the time is 4-10 hours.
6. catalyst according to claim 4, wherein the weight ratio of the dosage of the esters of silicon acis and the template is 1:
1-1.5。
7. catalyst according to claim 4, wherein the silica zeolite carrier is hexagonal flake, and the total silicon
The particle diameter of molecular sieve carrier is 0.1-0.3 microns, and specific surface area is 300-600 meters squared per gram, most probable pore size 0.4-
0.6 nanometer, pore volume 0.1-0.2cm3/g。
8. the preparation method of load-type iron-based composite metal catalyst described in any one of claim 1-7, wherein the party
Method include: by silica zeolite carrier impregnation in the solution containing source of iron, so that iron component is supported on the silica zeolite and carry
On body, the source of iron contains Fe and M, wherein one of M Mn, K, Na, S, Cu and Zn or a variety of.
9. according to the method described in claim 8, wherein, the source of iron is the mixture of ferric nitrate, manganese nitrate and potassium nitrate.
10. the condition of the dipping includes: that temperature is 10-80 DEG C according to the method described in claim 8, wherein, the time is
0.1-1 hours.
11. according to the method described in claim 9, wherein, source of iron dissolution is configured in deionized water containing source of iron
Solution, the dosage of the and deionized water relative to 100ml, the ferric nitrate is 0.7-2.1 grams, and the dosage of the manganese nitrate is
0.41-1.23 grams, the dosage of the potassium nitrate is 0.18-0.54 grams.
12. catalyst made from preparation method described in any one of claim 8-11.
13. catalyst described in any one of claim 1-7 and 12 is directly preparing answering in low-carbon alkene using synthesis gas
With.
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| CN111036282B (en) * | 2018-10-15 | 2022-09-27 | 中国石油化工股份有限公司 | Supported catalyst, preparation method thereof and method for preparing alpha-olefin from synthesis gas |
| CN111068689B (en) * | 2018-10-18 | 2023-04-07 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin by direct synthesis gas method and application thereof |
| CN111672537B (en) * | 2020-06-05 | 2023-07-14 | 北京石油化工学院 | Supported Fe-X/NaY catalyst and preparation method and application thereof |
| CN113856740A (en) * | 2020-06-30 | 2021-12-31 | 中国石油化工股份有限公司 | Catalyst with function of catalytically preparing low-carbon hydrocarbon, application of catalyst and method for preparing low-carbon hydrocarbon from hydrogen-poor synthesis gas |
| CN112517066B (en) * | 2020-12-18 | 2022-02-01 | 武汉大学 | Supported nano iron-based catalyst and preparation method and application thereof |
| CN115228507B (en) * | 2021-04-23 | 2023-08-22 | 中国石油化工股份有限公司 | Catalyst with deoxidizing function and preparation method and application thereof |
| CN115475651B (en) * | 2021-06-16 | 2024-03-29 | 中国石油化工股份有限公司 | Non-noble metal catalyst for dehydrogenation reaction and method for dehydrogenating low-carbon alkane |
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