CN112044446A - Catalyst and preparation method and application thereof - Google Patents

Catalyst and preparation method and application thereof Download PDF

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CN112044446A
CN112044446A CN202010985803.2A CN202010985803A CN112044446A CN 112044446 A CN112044446 A CN 112044446A CN 202010985803 A CN202010985803 A CN 202010985803A CN 112044446 A CN112044446 A CN 112044446A
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定明月
徐艳飞
马光远
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Shenzhen Research Institute of Wuhan University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/397—Egg shell like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/033—Using Hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

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  • General Chemical & Material Sciences (AREA)
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Abstract

The invention provides a catalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps: dissolving ferrous salt and polyvinylpyrrolidone in water; then adding a precipitator and then adding potassium permanganate, aging and centrifugally separating to obtain first powder; dispersing the first powder in an alcohol solvent, then adding a silicon source, adding ammonia water and water, stirring for reaction, and then carrying out centrifugal separation to obtain the catalyst. The preparation method of the catalyst has simple preparation process and is suitable for large-scale industrial production; the prepared catalyst is of a double-shell structure, and a manganese shell is beneficial to electron transfer between manganese and iron, so that the selectivity of olefin in the product is improved; the confinement effect of the silicon shell is beneficial to carbon chain growth reaction, and the selectivity of the liquid fuel is improved; the catalyst with the double-layer shell structure can convert the synthetic gas into the liquid fuel rich in olefin at high selectivity, and has good industrial application prospect.

Description

Catalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of catalysts, and particularly relates to a catalyst and a preparation method and application thereof.
Background
People can not leave liquid fuel on daily trips. At present, gasoline, diesel oil and aviation fuel oil are mainly extracted from petroleum. However, with the rapid development of economy, the demand of people for liquid fuel is increasing, and petroleum resources are gradually exhausted. The severe energy situation requires us to find a future alternative to petroleum and develop a new way to produce liquid fuels from other carbon resources. China has abundant coal and biomass resources, and the coal and biomass resources are pyrolyzed and converted into synthesis gas (carbon monoxide (CO) and hydrogen (H)2) And the synthesis gas is converted into high-quality liquid fuel through a Fischer-Tropsch synthesis reaction (Fischer-Tropsch synthesis is a process for converting the synthesis gas into various chemicals or liquid fuels under a catalyst and appropriate reaction conditions), which may be a way to replace petroleum.
The core problem in the process of efficiently converting syngas to liquid fuels is the design of the catalyst. The prior art discloses iron oxide particles coated with a carbon shell, and the confinement effect of the carbon shell is found to be beneficial to the generation of liquid fuel, and the selectivity of gasoline can reach 43.4%. However, the selectivity of the carbon shell coated iron oxide particles is not high.
In the actual production process, higher target product selectivity is beneficial to reducing energy consumption in the product separation process and increasing product income. How to further improve the selectivity of the liquid fuel in the conversion process of the synthesis gas and ensure that the liquid fuel is rich in high-octane olefins or isoparaffins remains a challenge in the field of fischer-tropsch synthesis.
Disclosure of Invention
In view of the above, the present invention provides a catalyst, a preparation method and an application thereof, so as to improve the selectivity of liquid fuel.
In a first aspect, the present invention provides a method for preparing a catalyst, comprising the steps of:
dissolving ferrous salt and polyvinylpyrrolidone in water;
then adding a precipitator and then adding potassium permanganate, aging and centrifugally separating to obtain first powder;
dispersing the first powder in an alcohol solvent, then adding a silicon source, adding ammonia water and water, stirring for reaction, and then carrying out centrifugal separation to obtain the catalyst.
Optionally, in the preparation method of the catalyst, the ferrous salt is ferrous chloride or ferrous sulfate; the precipitator comprises one of sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide; the alcohol solvent is ethanol.
Optionally, in the preparation method of the catalyst, the molar ratio of potassium permanganate to ferrous salt is 0.1-3: 1.
Optionally, in the preparation method of the catalyst, the silicon source is ethyl silicate, and the volume-to-mass ratio of the ethyl silicate to the first powder is 0.1-5 ml:1 g.
Optionally, the preparation method of the catalyst comprises the steps of dissolving ferrous salt and polyvinylpyrrolidone in water, heating to 35-95 ℃, adding a precipitator, adding potassium permanganate, aging for 0.5-24 hours, and performing centrifugal separation to obtain first powder.
Optionally, in the preparation method of the catalyst, the volume ratio of the ethyl silicate to the ammonia water is 1: 0.8-100.
In a second aspect, the invention also provides a catalyst prepared by the preparation method, and the catalyst comprises a ferroferric oxide core layer, a first manganese dioxide shell layer coated on the periphery of the ferroferric oxide core layer and a second silicon dioxide shell layer coated on the periphery of the first manganese dioxide shell layer.
In a third aspect, the invention also provides the use of the catalyst in the conversion of synthesis gas to liquid fuel via a Fischer-Tropsch synthesis reaction.
Compared with the prior art, the preparation method of the catalyst has the following beneficial effects:
the preparation method of the catalyst provided by the invention comprises the steps of dissolving ferrous salt and polyvinylpyrrolidone in water, and then reacting with potassium permanganate to obtain first powder Fe3O4@MnO2(ii) a Then the first powder Fe3O4@MnO2In alcohol solvent, silicon source is added and reacted to obtain catalyst, and the preparation process is simpleThe method is suitable for large-scale industrial production; the prepared catalyst is of a double-shell structure, and a manganese shell is beneficial to electron transfer between manganese and iron, so that the selectivity of olefin in the product is improved; the confinement effect of the silicon shell is beneficial to carbon chain growth reaction, and the selectivity of the liquid fuel is improved; the catalyst with the double-layer shell structure can convert the synthetic gas into the liquid fuel rich in olefin at high selectivity, and has good industrial application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a process flow diagram of a method of making a catalyst of the present invention;
FIG. 2 is an XRD pattern of the catalyst prepared in example 1 of the present invention;
FIG. 3 is a transmission electron micrograph of the catalyst prepared in comparative example 1;
FIG. 4 is Fe3O4And Fe prepared in comparative example 13O4@MnO2XPS spectra of (a);
FIG. 5 is a transmission electron micrograph of the catalyst prepared in example 1.
Detailed Description
In the following, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The invention provides a preparation method of a catalyst, which comprises the following steps as shown in figure 1:
s1, dissolving ferrous salt and polyvinylpyrrolidone in water;
s2, adding a precipitator, adding potassium permanganate, aging, and performing centrifugal separation to obtain first powder;
s3, dispersing the first powder in an alcohol solvent, then adding a silicon source, adding ammonia water and water, stirring for reaction, and then carrying out centrifugal separation to obtain the catalyst.
It should be noted that, in the embodiment of the present application, the ferrous salt is ferrous chloride or ferrous sulfate; the precipitant is alkali or strong alkali weak acid salt, and specifically comprises one of sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide; the alcohol solvent is ethanol; the silicon source is ethyl silicate.
Specifically, in this embodiment of the present application, S1 specifically includes: 27.8g of ferrous sulfate heptahydrate and 100g of polyvinylpyrrolidone are weighed, dissolved in 1L of water, and then heated to 35 ℃; s2 specifically includes: then adding 16g of sodium hydroxide and 15.8g of potassium permanganate, aging for 24h, centrifugally separating, washing and drying to obtain Fe with ferroferric oxide as a nuclear layer and manganese oxide as a shell layer3O4@MnO2Namely the first powder; s3 specifically includes: dispersing 5g of the first powder in ethanol, adding 25mL of ethyl silicate, adding 20mL of ammonia water and 80mL of water, stirring for 24h, performing centrifugal separation, washing and drying to obtain double-shell coated ferroferric oxide Fe3O4@MnO2@SiO2(ferroferric oxide is a core layer, manganese dioxide coated on the periphery of the ferroferric oxide core layer is used as a first shell layer, and silicon oxide coated on the periphery of the manganese dioxide is used as a second shell layer), namely the catalyst.
According to the preparation method of the catalyst provided by the embodiment of the application, ferrous salt and polyvinylpyrrolidone are dissolved in water, and then potassium permanganate reacts to obtain first powder Fe3O4@MnO2(ii) a Then the first powder Fe3O4@MnO2In the alcohol solvent, a silicon source is added, and the catalyst is obtained through reaction, so that the preparation process is simple, and the method is suitable for large-scale industrial production; the prepared catalyst is of a double-shell structure, and the manganese shell is beneficial to manganese andelectron transfer between iron improves the selectivity of olefin in the product; the confinement effect of the silicon shell is beneficial to carbon chain growth reaction, and the selectivity of the liquid fuel is improved; the catalyst with the double-layer shell structure can convert the synthetic gas into the liquid fuel rich in olefin at high selectivity, and has good industrial application prospect.
Based on the same inventive concept, the embodiment of the application also provides a catalyst prepared by the preparation method, and the catalyst comprises a ferroferric oxide core layer, a first manganese dioxide shell layer coated on the periphery of the ferroferric oxide core layer and a second silicon dioxide shell layer coated on the periphery of the first manganese dioxide shell layer. Namely, the catalyst takes ferroferric oxide as a core layer, manganese dioxide coated on the periphery of the ferroferric oxide core layer as a first shell layer, and silicon oxide coated on the periphery of the manganese dioxide as a second shell layer.
Based on the same inventive concept, the embodiment of the application also provides the application of the catalyst in the conversion of the synthesis gas into the liquid fuel through the Fischer-Tropsch synthesis reaction.
Example 2
The invention provides a preparation method of a catalyst, which comprises the following steps as shown in figure 1:
s1, weighing 6.95g of ferrous sulfate heptahydrate and 30g of polyvinylpyrrolidone, dissolving in 1L of water, and heating to 95 ℃;
s2, adding 10g of sodium hydroxide and 7.9g of potassium permanganate, aging for 0.5h, centrifugally separating, washing and drying to obtain Fe with ferroferric oxide as a nuclear layer and manganese oxide as a shell layer3O4@MnO2Namely the first powder;
s3, dispersing 1g of first powder in ethanol, adding 0.1mL of ethyl silicate, adding 10mL of ammonia water and 50mL of water, stirring for 0.5h, centrifugally separating, washing and drying to obtain double-shell coated ferroferric oxide Fe3O4@MnO2@SiO2(ferroferric oxide is a core layer, manganese dioxide coated on the periphery of the ferroferric oxide core layer is used as a first shell layer, and silicon oxide coated on the periphery of the manganese dioxide is used as a second shell layer), namely the catalyst.
Based on the same inventive concept, the embodiment of the application also provides a catalyst prepared by the preparation method, and the catalyst comprises a ferroferric oxide core layer, a first manganese dioxide shell layer coated on the periphery of the ferroferric oxide core layer and a second silicon dioxide shell layer coated on the periphery of the first manganese dioxide shell layer. Namely, the catalyst takes ferroferric oxide as a core layer, manganese dioxide coated on the periphery of the ferroferric oxide core layer as a first shell layer, and silicon oxide coated on the periphery of the manganese dioxide as a second shell layer.
Based on the same inventive concept, the embodiment of the application also provides the application of the catalyst in the conversion of the synthesis gas into the liquid fuel through the Fischer-Tropsch synthesis reaction.
Example 3
The invention provides a preparation method of a catalyst, which comprises the following steps as shown in figure 1:
s1, weighing 4.98g of ferrous chloride tetrahydrate and 20g of polyvinylpyrrolidone, dissolving in 500mL of water, and heating to 65 ℃;
s2, adding 5g of sodium carbonate and 11.86g of potassium permanganate, aging for 5h, centrifugally separating, washing and drying to obtain Fe with ferroferric oxide as a core layer and manganese oxide as a shell layer3O4@MnO2Namely the first powder;
s3, dispersing 1g of first powder in ethanol, adding 1mL of ethyl silicate, adding 5mL of ammonia water and 10mL of water, stirring for 5 hours, centrifugally separating, washing and drying to obtain double-shell coated ferroferric oxide Fe3O4@MnO2@SiO2(ferroferric oxide is a core layer, manganese dioxide coated on the periphery of the ferroferric oxide core layer is used as a first shell layer, and silicon oxide coated on the periphery of the manganese dioxide is used as a second shell layer), namely the catalyst.
Based on the same inventive concept, the embodiment of the application also provides a catalyst prepared by the preparation method, and the catalyst comprises a ferroferric oxide core layer, a first manganese dioxide shell layer coated on the periphery of the ferroferric oxide core layer and a second silicon dioxide shell layer coated on the periphery of the first manganese dioxide shell layer. Namely, the catalyst takes ferroferric oxide as a core layer, manganese dioxide coated on the periphery of the ferroferric oxide core layer as a first shell layer, and silicon oxide coated on the periphery of the manganese dioxide as a second shell layer.
Based on the same inventive concept, the embodiment of the application also provides the application of the catalyst in the conversion of the synthesis gas into the liquid fuel through the Fischer-Tropsch synthesis reaction.
Example 4
The invention provides a preparation method of a catalyst, which comprises the following steps as shown in figure 1:
s1, weighing 7.47g of ferrous chloride tetrahydrate and 20g of polyvinylpyrrolidone, dissolving in 500mL of water, and heating to 75 ℃;
s2, adding 5g of potassium carbonate and 2.97g of potassium permanganate, aging for 12h, centrifugally separating, washing and drying to obtain Fe with ferroferric oxide as a nuclear layer and manganese oxide as a shell layer3O4@MnO2Namely the first powder;
s3, dispersing 0.5g of first powder in ethanol, adding 2mL of ethyl silicate, adding 10mL of ammonia water and 20mL of water, stirring for 12h, centrifugally separating, washing and drying to obtain double-shell coated ferroferric oxide Fe3O4@MnO2@SiO2(ferroferric oxide is a core layer, manganese dioxide coated on the periphery of the ferroferric oxide core layer is used as a first shell layer, and silicon oxide coated on the periphery of the manganese dioxide is used as a second shell layer), namely the catalyst.
Based on the same inventive concept, the embodiment of the application also provides a catalyst prepared by the preparation method, and the catalyst comprises a ferroferric oxide core layer, a first manganese dioxide shell layer coated on the periphery of the ferroferric oxide core layer and a second silicon dioxide shell layer coated on the periphery of the first manganese dioxide shell layer. Namely, the catalyst takes ferroferric oxide as a core layer, manganese dioxide coated on the periphery of the ferroferric oxide core layer as a first shell layer, and silicon oxide coated on the periphery of the manganese dioxide as a second shell layer.
Based on the same inventive concept, the embodiment of the application also provides the application of the catalyst in the conversion of the synthesis gas into the liquid fuel through the Fischer-Tropsch synthesis reaction.
Example 5
The invention provides a preparation method of a catalyst, which comprises the following steps as shown in figure 1:
s1, 0.747g of ferrous chloride tetrahydrate and 5g of polyvinylpyrrolidone are weighed, dissolved in 100mL of water, and then heated to 40 ℃;
s2, adding 0.5g of potassium hydroxide and 0.059g of potassium permanganate, aging for 2h, centrifugally separating, washing and drying to obtain Fe with ferroferric oxide as a nuclear layer and manganese oxide as a shell layer3O4@MnO2Namely the first powder;
s3, dispersing 2g of the first powder in ethanol, adding 1mL of ethyl silicate, adding 15mL of ammonia water and 20mL of water, stirring for 12 hours, centrifugally separating, washing and drying to obtain double-shell coated ferroferric oxide Fe3O4@MnO2@SiO2(ferroferric oxide is a core layer, manganese dioxide coated on the periphery of the ferroferric oxide core layer is used as a first shell layer, and silicon oxide coated on the periphery of the manganese dioxide is used as a second shell layer), namely the catalyst.
Based on the same inventive concept, the embodiment of the application also provides a catalyst prepared by the preparation method, and the catalyst comprises a ferroferric oxide core layer, a first manganese dioxide shell layer coated on the periphery of the ferroferric oxide core layer and a second silicon dioxide shell layer coated on the periphery of the first manganese dioxide shell layer. Namely, the catalyst takes ferroferric oxide as a core layer, manganese dioxide coated on the periphery of the ferroferric oxide core layer as a first shell layer, and silicon oxide coated on the periphery of the manganese dioxide as a second shell layer.
Based on the same inventive concept, the embodiment of the application also provides the application of the catalyst in the conversion of the synthesis gas into the liquid fuel through the Fischer-Tropsch synthesis reaction.
Example 6
The invention provides a preparation method of a catalyst, which comprises the following steps as shown in figure 1:
s1, weighing 1.04g of ferrous sulfate heptahydrate and 2g of polyvinylpyrrolidone, dissolving in 100mL of water, and heating to 80 ℃;
s2, adding 1g of potassium carbonate and 0.177g of potassium permanganate, and agingDissolving for 12h, centrifugally separating, washing and drying to obtain Fe with ferroferric oxide as a nuclear layer and manganese oxide as a shell layer3O4@MnO2Namely the first powder;
s3, dispersing 5g of first powder in ethanol, adding 0.5mL of ethyl silicate, adding 3mL of ammonia water and 6mL of water, stirring for 2 hours, centrifugally separating, washing and drying to obtain double-shell coated ferroferric oxide Fe3O4@MnO2@SiO2(ferroferric oxide is a core layer, manganese dioxide coated on the periphery of the ferroferric oxide core layer is used as a first shell layer, and silicon oxide coated on the periphery of the manganese dioxide is used as a second shell layer), namely the catalyst.
Based on the same inventive concept, the embodiment of the application also provides a catalyst prepared by the preparation method, and the catalyst comprises a ferroferric oxide core layer, a first manganese dioxide shell layer coated on the periphery of the ferroferric oxide core layer and a second silicon dioxide shell layer coated on the periphery of the first manganese dioxide shell layer. Namely, the catalyst takes ferroferric oxide as a core layer, manganese dioxide coated on the periphery of the ferroferric oxide core layer as a first shell layer, and silicon oxide coated on the periphery of the manganese dioxide as a second shell layer.
Based on the same inventive concept, the embodiment of the application also provides the application of the catalyst in the conversion of the synthesis gas into the liquid fuel through the Fischer-Tropsch synthesis reaction.
Comparative example 1
A method of preparing a catalyst comprising the steps of: weighing 6.95g of ferrous sulfate heptahydrate and 30g of polyvinylpyrrolidone, dissolving in 1L of water, and heating to 95 ℃; then adding 10g of sodium hydroxide and 7.9g of potassium permanganate, aging for 0.5h, centrifugally separating, washing and drying to obtain Fe with ferroferric oxide as a nuclear layer and manganese oxide as a shell layer3O4@MnO2I.e. the catalyst.
The XRD pattern of the catalyst prepared in example 1 was measured, and the result is shown in fig. 2, and it can be seen from fig. 2 that the fe and mn elements in the catalyst exist as phases of magnetite and manganese dioxide, respectively, and no diffraction peak of silica exists in the figure, indicating that silica exists as an amorphous phase.
The transmission electron microscope images of the catalysts prepared in comparative example 1 were tested, and the results are shown in fig. 3, from the corresponding element distribution in fig. 3, it can be seen that the iron element is more intensively distributed in the interior of the catalyst, and the manganese element is more intensively distributed on the outer surface of the catalyst, demonstrating that the Fe prepared in comparative example 13O4@MnO2Is a core-shell structure of manganese oxide coated ferroferric oxide.
Testing of Fe3O4And Fe prepared in comparative example 13O4@MnO2The XPS spectrum of (A) is shown in FIG. 4, and it is understood from FIG. 4 that the spectrum is comparable to Fe3O4，Fe3O4@MnO2The binding energy of the medium iron element shifts to low energy, which indicates that the core-shell structure is favorable for electron transfer between manganese and iron.
Test of the catalyst Fe prepared in example 13O4@MnO2@SiO2The transmission electron micrograph of (1) shows that FIG. 5 shows that Fe is present in FIG. 53O4@MnO2Coated with a uniform amorphous silica shell, as demonstrated by the combination of FIGS. 2, 3 and 5, a double shell coated ferroferric oxide Fe3O4@MnO2@SiO2Successful preparation of the catalyst.
The catalysts obtained in example 1 and comparative example 1 were each tested for Fe3O4Selectivity to liquid fuels and olefins in the conversion of synthesis gas to liquid fuels via fischer-tropsch synthesis reaction.
The specific synthesis method comprises the following steps: 0.5g of the three catalysts are respectively weighed, then evenly mixed with 0.5g of quartz sand, and filled in a fixed bed reactor. Before each reaction, the catalyst is reduced in pure hydrogen at 350 ℃ for 10 hours, and then the temperature of the reactor is reduced to 200 ℃. Synthesis gas (47.5% CO/47.5% H) was passed through2/5％N2) The performance of the Fischer-Tropsch synthesis reaction was evaluated by raising the reaction pressure to 2MPa and the temperature to 320 ℃ and the results are shown in Table 1.
TABLE 1 Selectivity of different catalysts for liquid fuels and olefins
Figure BDA0002689163310000081
Figure BDA0002689163310000091
CH in Table 14、C2-4And C5+The sum of the selectivities of (a) is 100%, olefin selectivity refers to the content of olefin in the product.
As can be seen from Table 1, Fe prepared in comparative example 1 is comparable to ferroferric oxide3O4@MnO2Manganese dioxide coated catalyst vs. liquid fuel (C)5+Product) and olefin selectivity are significantly increased. Compared with single-layer manganese dioxide coated Fe3O4@MnO2The double-shell coated ferroferric oxide Fe prepared in example 1 of the present application3O4@MnO2@SiO2For liquid fuel (C)5+Product) and olefins, thus indicating a double shell coated ferroferric oxide, Fe3O4@MnO2@SiO2The catalyst can convert the synthesis gas into the liquid fuel rich in olefin with higher selectivity.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (8)

1. A preparation method of a catalyst is characterized by comprising the following steps:
dissolving ferrous salt and polyvinylpyrrolidone in water;
then adding a precipitator and then adding potassium permanganate, aging and centrifugally separating to obtain first powder;
dispersing the first powder in an alcohol solvent, then adding a silicon source, adding ammonia water and water, stirring for reaction, and then carrying out centrifugal separation to obtain the catalyst.
2. The method of claim 1, wherein the ferrous salt is ferrous chloride or ferrous sulfate; the precipitator comprises one of sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide; the alcohol solvent is ethanol.
3. The preparation method of the catalyst according to claim 1, wherein the molar ratio of potassium permanganate to ferrous salt is 0.1-3: 1.
4. The method for preparing the catalyst according to claim 1, wherein the silicon source is ethyl silicate, and the volume mass ratio of the ethyl silicate to the first powder is 0.1-5 ml:1 g.
5. The preparation method of the catalyst according to claim 1, wherein the ferrous salt and the polyvinylpyrrolidone are dissolved in water, the temperature is raised to 35-95 ℃, then the precipitant is added, the potassium permanganate is added, the aging is carried out for 0.5-24 h, and the first powder is obtained after centrifugal separation.
6. The method for preparing the catalyst according to claim 4, wherein the volume ratio of the ethyl silicate to the ammonia water is 1: 0.8-100.
7. The catalyst is characterized by being prepared by the preparation method of any one of claims 1 to 6, and the catalyst comprises a ferroferric oxide core layer, a first manganese dioxide shell layer coated on the periphery of the ferroferric oxide core layer and a second silicon dioxide shell layer coated on the periphery of the first manganese dioxide shell layer.
8. Use of a catalyst according to claim 7 in the conversion of synthesis gas to liquid fuel via a Fischer-Tropsch synthesis reaction.
CN202010985803.2A 2020-09-18 2020-09-18 Catalyst and preparation method and application thereof Pending CN112044446A (en)

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Application publication date: 20201208