CN112517066A - Supported nano iron-based catalyst and preparation method and application thereof - Google Patents
Supported nano iron-based catalyst and preparation method and application thereof Download PDFInfo
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- 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
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Abstract
The invention relates to a supported nano iron-based catalyst and a preparation method and application thereof. The method comprises the steps of taking hydrated iron oxide colloid particles as an active component precursor, enabling the hydrated iron oxide colloid particles to be adsorbed to the surface of a silicon oxide-based carrier, roasting to obtain supported nano iron oxide, and reducing to obtain a supported nano iron catalyst for Fischer-Tropsch synthesis reaction. The catalyst iron prepared by the method has the particle size of less than 20nm and narrow particle size distribution. In the Fischer-Tropsch synthesis reaction, compared with the iron-based catalyst prepared by the traditional impregnation method, the catalyst has higher CO conversion rate and low-carbon olefin selectivity, and better catalytic activity stability.
Description
Technical Field
The invention belongs to the field of petrochemical industry, and particularly belongs to the field of preparing low-carbon olefin by Fischer-Tropsch synthesis based on a supported iron-based catalyst.
Background
The low-carbon olefin (including ethylene, propylene and butylene) is the most basic raw material for petrochemical production and is the basis for producing other organic chemical products. The existing methods for preparing olefin can be generally divided into two main categories: the first is petroleum route, and the second is non-petroleum route. The shortage of petroleum resources is increasing, and the demand of people for light olefins is increasing dramatically, so that the synthesis of light olefins through non-petroleum routes is important. Based on the energy structure of rich coal, lean oil and less gas in China, the method has important significance for directly preparing the low-carbon olefin (FTO) by Fischer-Tropsch synthesis through the synthesis gas by taking coal, biomass and the like as raw materials. The key to the process is the development of an economical, efficient catalyst. The iron-based catalyst has low price, high strength, strong anti-poisoning performance and reaction gas H2: c is larger than the adjustable space, and the like, and is widely applied to FTO reaction.
The Fe-based catalysts currently used for FTO reactions are mainly supported and unsupported. The non-supported catalyst is easy to form a large amount of carbon deposition in industrial production. On one hand, the generation of carbon deposition can block the active sites of the catalyst to cause the activity of the catalyst to be reduced, and the catalyst needs frequent carbon burning regeneration, so that the cost of the process can be increased; on the other hand, the active particles of the unsupported catalyst are easy to break, and the mechanical stability is poor. Therefore, the supported iron-based catalyst is mainly used in the actual production at present, and the research of the catalyst with high conversion rate, high value-added product selectivity and good activity stability is the current research direction. In order to improve the FTO catalytic reaction performance of the supported catalyst and reduce the cost, more and more research efforts are being made to improve the dispersion degree of the metal active component to expose more active sites and improve the utilization rate of the metal active component.
The Fischer-Tropsch synthesis is a structure sensitive reaction, and the conversion rate of reactants and the selectivity of products are closely related to the particle size of a catalytic active component. Generally speaking, nanocrystallization of the catalytically active component favors higher reactant conversions, while uniformity of the particle size of the active particles favors high selectivity for a particular product. The traditional impregnation method is difficult to obtain the supported nano catalyst with high dispersion and uniform particle size. Chinese patent CN107754814B discloses the application of an iron-based catalyst in the Fischer-Tropsch synthesis of alcohol compounds, the active component of the catalyst is a composite oxide of Fe, Cu and Pd, and Al is deposited on the surface of the active component by adopting an atomic layer deposition method2O3、SiO2、TiO2And the like, but the method has complex experimental flow and higher requirement on production equipment. Chinese patent CN103464159A discloses a copper-iron based catalyst and application thereof in catalyzing synthesis gas to prepare low-carbon mixed alcohol, wherein a copper-magnesium-iron hydrotalcite precursor is prepared by adopting a nucleation crystallization isolation method, and then the precursor is roasted and reduced to obtain the copper-iron based catalyst with high-dispersion nano particles. However, the catalyst needs to be crystallized for 24-48h under the conditions of 100-. Chinese patent CN103203234A discloses a preparation method of a high-dispersion supported nano-metal Fe-based catalyst, but the method also needs to crystallize in a hydrothermal reaction kettle at the temperature of 80-150 ℃ for 2-6h and needs to crystallize in N2/H2/CH4Roasting under the condition of mixed gas to obtain the high-dispersion iron-based nano catalyst. Therefore, the preparation of the nano iron-based Fischer-Tropsch synthesis catalyst with a simple method and low cost is still the goal pursued by the industry. The document (environ. sci. technol.2012,46, 12648-.
Disclosure of Invention
The invention aims to provide a simple and efficient preparation method of a supported nano iron-based catalyst, which is used for preparing low-carbon olefin by Fischer-Tropsch synthesis.
The scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a supported nano iron-based catalyst comprises the following preparation steps:
(1) reacting ferric salt with alkali in water solution to obtain ferric hydroxide precipitate, filtering or centrifuging, adding acetic acid into the wet precipitate, and stirring to form ferric oxide hydrate colloidal solution;
(2) adding a silica-based carrier into the hydrated ferric oxide colloidal solution prepared in the step (1), and stirring to enable colloidal particles to be adsorbed on the surface of the carrier;
(3) after separating the solid and the liquid in the step (2), washing the solid with pure water, and drying and roasting to obtain the supported nano iron-based catalyst;
(4) and (3) taking the supported nano iron-based catalyst obtained in the step (3) as a carrier, and repeating the steps (1), (2) and (3) for 0 or more times to obtain the supported nano iron-based catalyst with higher loading capacity.
Preferably, the silica-based carrier comprises porous silica gel, mesoporous silica, fibrous nano-silica, diatomite, silica nanospheres and a molecular sieve; the roasting temperature is 300-600 ℃; the reduction temperature is 300-600 ℃.
A preparation method of an assistant metal modified load type nanometer iron-based catalyst comprises the following preparation steps:
(1) reacting ferric salt with alkali in water solution to obtain ferric hydroxide precipitate, filtering or centrifuging, adding acetic acid into the wet precipitate, and stirring to form ferric oxide hydrate colloidal solution;
(2) preparing a hydrated oxide colloidal solution of the auxiliary metal M by the same method in the step (1);
(3) adding a silica-based carrier into the hydrated ferric oxide colloidal solution prepared in the step (1), and stirring to enable colloidal particles to be adsorbed on the surface of the carrier;
(4) after separating the solid and the liquid in the step (3), washing the solid with pure water, and drying and roasting to obtain supported nano iron oxide;
(5) taking the loaded nano ferric oxide obtained in the step (4) as a carrier, and repeating the steps (1), (3) and (4) for 0 or more times to obtain the loaded nano ferric oxide with higher loading capacity;
(6) and (3) adding the supported nano iron oxide obtained in the step (4) or (5) as a carrier into the hydrated oxide colloidal solution of the assistant metal M obtained in the step (2), stirring to enable hydrated oxide colloidal particles of the metal M to be adsorbed on the surface of the carrier, separating solids, washing, drying and roasting to obtain the assistant metal M modified supported nano iron-based catalyst.
Preferably, the promoter metal M is manganese or cobalt; and (3) when the metal M is cobalt, stirring in air after the cobalt hydroxide precipitate obtained in the step (2) is oxidized, filtering or centrifuging, adding acetic acid into the wet precipitate, and stirring until a hydrated cobalt oxide colloidal solution is formed.
Preferably, the silica-based carrier comprises porous silica gel, mesoporous silica, fibrous nano-silica, diatomite, silica nanospheres and a molecular sieve; the roasting temperature is 300-600 ℃; the reduction temperature is 300-600 ℃.
The invention also provides a preparation method of another assistant metal modified load type nanometer iron-based catalyst, which comprises the following preparation steps:
(1) reacting ferric salt with alkali in water solution to obtain ferric hydroxide precipitate, filtering or centrifuging, adding acetic acid into the wet precipitate, and stirring to form ferric oxide hydrate colloidal solution;
(2) adding a silica-based carrier into the hydrated ferric oxide colloidal solution prepared in the step (1), and stirring to enable colloidal particles to be adsorbed on the surface of the carrier;
(3) after separating the solid and the liquid in the step (2), washing the solid with pure water, and drying and roasting to obtain supported nano iron oxide;
(4) taking the loaded nano ferric oxide obtained in the step (3) as a carrier, and repeating the steps (1), (2) and (3) for 0 or more times to obtain the loaded nano ferric oxide with higher loading capacity;
(5) and (4) taking the supported nano iron oxide obtained in the step (3) or (4) as a carrier, dipping a salt solution of an auxiliary metal N onto the carrier, and drying and roasting to obtain the auxiliary metal N modified supported nano iron-based catalyst.
Preferably, the promoter metal N comprises zirconium, manganese, cobalt, magnesium, calcium, potassium and sodium.
Preferably, the silica-based carrier comprises porous silica gel, mesoporous silica, fibrous nano-silica, diatomite, silica nanospheres and a molecular sieve; the roasting temperature is 300-600 ℃; the reduction temperature is 300-600 ℃.
The invention also aims to provide a supported nano iron-based catalyst prepared by the method.
The invention also aims to provide the application of the supported nano iron-based catalyst, wherein the supported nano iron-based catalyst is reduced by using carbon monoxide or hydrogen and is used for preparing low-carbon olefin by Fischer-Tropsch synthesis.
The catalyst of the invention has the characteristics and advantages that:
(1) the hydrated iron oxide colloidal particles are positively charged, and under a certain pH value condition (the pH value is more than 3.5), the surface of the silicon oxide carrier is negatively charged, the colloidal particles are easily dispersed and adsorbed on adsorption sites on the surface of the carrier through electrostatic action, the load can be adjusted by adjusting the adsorption quantity, and the particle size of the product iron particles is further adjusted.
(2) The catalyst is simple in preparation method, mild in preparation condition, easy to operate, wide in material source, low in cost and suitable for large-scale production, and is operated at normal temperature and normal pressure;
(3) the catalyst has high conversion rate to reactants and high selectivity to low-carbon olefin in the product, and is suitable for Fischer-Tropsch synthesis and other structure sensitive reactions.
Drawings
FIG. 1.20% FeHAc/SiO2A TEM image and a particle size distribution diagram of the catalyst, wherein (A) and (B) are respectively a TEM image and a particle size distribution diagram;
FIG. 2.20% FeHAc/SiO2XRD pattern of the catalyst;
FIG. 3.16% Fe/SiO2-TEM images of imp catalysts;
FIG. 4.16% Fe/SiO2-XRD pattern of imp catalyst;
FIG. 5.30% FeHAc/SiO2A TEM image and a particle size distribution diagram of the catalyst, wherein (C) and (D) are respectively a TEM image and a particle size distribution diagram;
FIG. 6.30% FeHAc/SiO2XRD pattern of the catalyst;
FIG. 7.24% Fe/SiO2-XRD pattern of imp catalyst;
FIG. 8.40% FeHAc/SiO2A TEM image and a particle size distribution diagram of the catalyst, wherein (E) and (F) are respectively a TEM image and a particle size distribution diagram;
FIG. 9.40% FeHAc/SiO2XRD pattern of the catalyst;
FIG. 10.30% Fe/SiO2-XRD pattern of imp catalyst;
FIG. 11.50% FeHAc/SiO2A TEM image and a particle size distribution diagram of the catalyst, wherein (G) and (H) are respectively a TEM image and a particle size distribution diagram;
FIG. 12.50% FeHAc/SiO2XRD pattern of the catalyst;
FIG. 13.40% FeHAc/SBA-15 catalyst TEM image and particle size distribution diagram, wherein (A), (B) are respectively TEM image and particle size distribution diagram;
FIG. 14.XRD pattern of 40% FeHAc/SBA-15 catalyst;
FIG. 15.40% of a TEM image and a particle size distribution chart of the FeHAc/KCC-1 catalyst, wherein (A), (B) are the TEM image and the particle size distribution chart, respectively;
FIG. 16.XRD pattern of 40% FeHAc/KCC-1 catalyst;
FIG. 17.40% FeHAc/SiO2-TEM and particle size distribution plots for NP catalysts, wherein (a), (B) are TEM and particle size distribution plots, respectively;
FIG. 18.40% FeHAc/SiO2-XRD pattern of NP catalyst;
FIG. 19.40% FeHAc/SiO2With 30% Fe/SiO2-CO conversion variation of imp catalyst in continuous 100 hours Fischer-Tropsch synthesis reaction.
Detailed Description
The following examples are provided to further illustrate the present invention for better understanding, but the present invention is not limited to the following examples.
In order to illustrate the present invention more clearly, the following examples are given without any limitation to the scope of the present invention.
Example 1
1.80g of Fe (NO)3)3·9H2Dissolving O in 20ml deionized water, stirring for 10min, slowly adding 12ml NaOH (1.18 mol. L)-1) Dissolving to obtain iron hydroxide precipitate, centrifuging to separate precipitate, adding acetic acid (molar ratio of acetic acid to Fe is 3:1) into wet precipitate, and stirring for 1 hr until forming hydrated ferric oxide colloid solution with pH of 3.7. Then, 1g of porous silica gel was added to the colloidal solution and stirred to adsorb colloidal particles to the surface of the carrier, followed by centrifugal separation and washing with pure water. After drying, roasting for 4h at 450 ℃ in air to obtain 20% FeHAc/SiO2Catalyst (catalyst 1). The actual loading of Fe was determined to be about 16%. TEM image (FIG. 1) shows Fe2O3The average particle diameter is 1.3nm, and the particle diameter distribution range is 0.6-1.9 nm. XRD pattern showed Fe2O3The peak was weak (FIG. 2), indicating that the particle size was small.
Example 2
As a comparison of catalyst 1, catalyst 2 was prepared in a similar loading using a conventional impregnation method. 1.15g of Fe (NO)3)3·9H2Dissolving O in 10ml deionized water, stirring for 10min, adding 1g porous silica gel carrier, stirring for 30min, stirring in 50 deg.C constant temperature water bath, evaporating, and calcining at 450 deg.C in air for 4 hr to obtain 16% Fe/SiO2Imp catalyst (catalyst 2), close to the actual loading of catalyst 1. The TEM images indicated that the loaded particles were not uniform in size (fig. 3). Fe in XRD pattern2O3The diffraction peak of (1) is very remarkable (figure 4), and Fe is obtained by calculation according to the Scherrer formula2O3Has an average particle size of 18.1nm and has an iron dispersibility significantly lower than that of catalyst 1.
Example 3
3.10g of Fe (NO)3)3·9H2Dissolving O in 30ml deionized water, stirring for 10min, slowly adding 18ml NaOH (1.18 mol. L)-1) Dissolving to obtain iron hydroxide precipitate, centrifuging to separate precipitate, adding acetic acid (molar ratio of acetic acid to Fe is 3:1) into wet precipitate, and stirring for 1 hr until forming hydrated ferric oxide colloid solution with pH of 3.7. Other preparation processes are the same as the catalyst 1 to obtain 30 percent of FeHAc/SiO2Catalyst (catalyst 3). Determination of Fe2O3The actual loading of (a) is about 24%. TEM image (FIG. 5) shows Fe2O3The average particle diameter is 3.4nm, and the particle diameter distribution range is 2.1-4.7 nm. XRD pattern showed Fe2O3The peak was weak (FIG. 6), indicating that the particle size was small.
Example 4
As a comparison to catalyst 3, catalyst 4 was prepared at a similar loading using a conventional impregnation method. 1.73g of Fe (NO)3)3·9H2Dissolving O in 15ml deionized water, stirring for 10min, adding 1g porous silica gel carrier, stirring for 30min, evaporating at 50 deg.C in a constant temperature water bath, drying at 60 deg.C for 6 hr, and calcining at 450 deg.C for 4 hr to obtain 24% Fe/SiO2Imp catalyst (catalyst 4). Fe in XRD pattern2O3The diffraction peak of (1) is very remarkable (figure 7), and Fe is calculated according to the Scherrer formula2O3The average particle size was 18.3nm and the iron dispersibility was significantly lower than catalyst 3.
Example 5
4.81g of Fe (NO)3)3·9H2O is dissolved in 40ml of deionized water, stirred for 10min and then slowly added with 24ml of NaOH (1.18 mol. L)-1) Dissolving to obtain iron hydroxide precipitate, centrifuging to separate precipitate, adding acetic acid (molar ratio of acetic acid to Fe is 3:1) into wet precipitate, and stirring for 1 hr until forming hydrated ferric oxide colloid solution with pH of 3.7. Other preparation processes are the same as the catalyst 1 to obtain 40 percent FeHAc/SiO2Catalyst (catalyst 5) and Fe measurement2O3The actual loading of (a) is about 30%. TEM image (FIG. 8) shows Fe2O3The average particle diameter is 4.7nm, and the particle diameter distribution range is 3.3-5.6nAnd m is selected. XRD pattern showed Fe2O3The peak was weak (FIG. 9), indicating that the particle size was small.
Example 6
As a comparison to catalyst 5, catalyst 6 was prepared at a similar loading using a conventional impregnation method. 2.16g of Fe (NO)3)3·9H2Dissolving O in 20ml deionized water, stirring for 10min, adding 1g porous silica gel carrier, stirring for 30min, evaporating at 50 deg.C in a constant temperature water bath, drying at 60 deg.C for 6 hr, and calcining at 450 deg.C for 4 hr to obtain 30% Fe/SiO2Imp catalyst (catalyst 6). Fe in XRD pattern2O3The diffraction peak of (1) is very remarkable (figure 10), and Fe is obtained by calculation according to the Scherrer formula2O3The average particle size was 19.2nm and the iron dispersibility was significantly lower than that of catalyst 5.
Example 7
7.21g of Fe (NO)3)3·9H2Dissolving O in 50ml deionized water, stirring for 10min, slowly adding 30ml NaOH (1.18 mol. L)-1) Dissolving to obtain iron hydroxide precipitate, centrifuging to separate precipitate, adding acetic acid (molar ratio of acetic acid to Fe is 3:1) into wet precipitate, and stirring for 1 hr until forming hydrated ferric oxide colloid solution with pH of 3.7. Other preparation processes are the same as the catalyst 1 to obtain 50 percent FeHAc/SiO2Catalyst (catalyst 7). Determination of Fe2O3The actual load amount of (c) was about 31%. TEM image (FIG. 11) shows Fe2O3The average particle diameter is 6.1nm, and the particle diameter distribution range is 4.7-6.9 nm. Fe on XRD pattern (FIG. 12)2O3The diffraction peaks were still weaker than those of catalysts 2,4 and 6 prepared by impregnation, indicating better dispersibility.
Example 8
4.81g of Fe (NO)3)3·9H2O is dissolved in 40ml of deionized water, stirred for 10min and then slowly added with 24ml of NaOH (1.18 mol. L)-1) Dissolving to obtain iron hydroxide precipitate, centrifuging to separate precipitate, adding acetic acid (molar ratio of acetic acid to Fe is 3:1) into wet precipitate, and stirring for 1 hr until forming ferric oxide hydrate colloidal solution. Then 1g of mesoporous silica SBA-15 is added to the colloidal solutionStirring in the solution to adsorb the colloidal particles onto the surface of the carrier. The other preparation process is the same as that of catalyst 1, and 40% FeHAc/SBA-15 catalyst (catalyst 8) is obtained. TEM image (FIG. 13) shows Fe2O3The average particle diameter is 4.6nm, and the particle diameter distribution range is 3.3-4.7 nm. XRD pattern showed Fe2O3The peak was weak (FIG. 14), indicating that the particle size was small.
Example 9
4.81g of Fe (NO)3)3·9H2O is dissolved in 40ml of deionized water, stirred for 10min and then slowly added with 24ml of NaOH (1.18 mol. L)-1) Dissolving to obtain iron hydroxide precipitate, centrifuging to separate precipitate, adding acetic acid (molar ratio of acetic acid to Fe is 3:1) into wet precipitate, and stirring for 1 hr until forming ferric oxide hydrate colloidal solution. Then 1g of fibrous nano-silica KCC-1 is added into the colloidal solution and stirred, so that the colloidal particles are adsorbed on the surface of the carrier. The other preparation process is the same as that of the catalyst 1, and the 40 percent FeHAc/KCC-1 catalyst (catalyst 9) is obtained. TEM image (FIG. 15) shows Fe2O3The average particle diameter is 3.9nm, and the particle diameter distribution range is 3.4-5.6 nm. XRD pattern showed Fe2O3The peak was weak (FIG. 16), indicating that the particle size was small.
Example 10
4.81g of Fe (NO)3)3·9H2O is dissolved in 40ml of deionized water, stirred for 10min and then slowly added with 24ml of NaOH (1.18 mol. L)-1) Dissolving to obtain iron hydroxide precipitate, centrifuging to separate precipitate, adding acetic acid (molar ratio of acetic acid to Fe is 3:1) into wet precipitate, and stirring for 1 hr until forming ferric oxide hydrate colloidal solution. Then 1g of silica nanosphere (SiO)2NP) is added to the colloidal solution and stirred to adsorb the colloidal particles to the surface of the carrier. Other preparation processes are the same as the catalyst 1 to obtain 40 percent FeHAc/SiO2NP catalyst (catalyst 10). TEM image (FIG. 17) shows Fe2O3The average particle diameter is 4.5nm, and the particle diameter distribution range is 3.5-5.5 nm. XRD pattern showed Fe2O3The peak was weak (FIG. 18), indicating that the particle size was small.
Example 11
4.81g of Fe (NO)3)3·9H2O is dissolved in 40ml of deionized water, stirred for 10min and then slowly added with 24ml of NaOH (1.18 mol. L)-1) Solution to obtain Fe (OH)xPrecipitating, separating precipitate by centrifugation, adding acetic acid (molar ratio of acetic acid to Fe is 3:1) into wet precipitate, and stirring for 1h until a hydrated iron oxide colloidal solution is formed. Then adding 1g of ZSM-5 molecular sieve into the colloidal solution, and stirring to enable colloidal particles to be adsorbed on the surface of the carrier. The other preparation process is the same as that of the catalyst 1, and 40 percent of FeHAc/ZSM-5 catalyst (catalyst 11) is obtained. TEM image showing Fe2O3The average grain diameter is 9.2nm, and the grain diameter distribution range is 8.6-11.4 nm.
Example 12
4.81g of Fe (NO)3)3·9H2O is dissolved in 40ml of deionized water, stirred for 10min and then slowly added with 24ml of NaOH (1.18 mol. L)-1) Solution to obtain Fe (OH)xPrecipitating, separating precipitate by centrifugation, adding acetic acid (molar ratio of acetic acid to Fe is 3:1) into wet precipitate, and stirring for 1h until a hydrated iron oxide colloidal solution is formed. Then adding 1g of beta molecular sieve into the colloidal solution, and stirring to enable colloidal particles to be adsorbed on the surface of the carrier. The other preparation process is the same as that of the catalyst 1, and 40 percent of FeHAc/Beta catalyst (catalyst 12) is obtained. TEM image showing Fe2O3The average particle diameter is 10.1nm, and the particle diameter distribution range is 9.2-13.2 nm.
Example 13
4.81g of Fe (NO)3)3·9H2O is dissolved in 40ml of deionized water, stirred for 10min and then slowly added with 24ml of NaOH (1.18 mol. L)-1) Solution to obtain Fe (OH)xPrecipitating, separating precipitate by centrifugation, adding acetic acid (molar ratio of acetic acid to Fe is 3:1) into wet precipitate, and stirring for 1h until a hydrated iron oxide colloidal solution is formed. Then, 1g of mesoporous silica KIT-6 is added into the colloidal solution and stirred, so that colloidal particles are adsorbed on the surface of the carrier. The other preparation process is the same as that of the catalyst 1, and 40 percent of FeHAc/KIT-6 catalyst (catalyst 13) is obtained. TEM image showing Fe2O3The average particle diameter is 5.3nm, and the particle diameter distribution range is 3.9-6.4 nm.
Example 14
4.81g of Fe (NO)3)3·9H2O is dissolved in 40ml of deionized water, stirred for 10min and then slowly added with 24ml of NaOH (1.18 mol. L)-1) Solution to obtain Fe (OH)xPrecipitating, separating precipitate by centrifugation, adding acetic acid (molar ratio of acetic acid to Fe is 3:1) into wet precipitate, and stirring for 1h until a hydrated iron oxide colloidal solution is formed. Then 1g of mesoporous silica MCM-41 is added into the colloidal solution and stirred, so that colloidal particles are adsorbed on the surface of the carrier. The other preparation process is the same as that of the catalyst 1, and 40 percent of FeHAc/MCM-41 catalyst (catalyst 14) is obtained. TEM image showing Fe2O3The average particle size was 2.7 nm. The particle size distribution range is 2.1-4.9 nm.
Example 15
4.81g of Fe (NO)3)3·9H2O is dissolved in 40ml of deionized water, stirred for 10min and then slowly added with 24ml of NaOH (1.18 mol. L)-1) Solution to obtain Fe (OH)xPrecipitating, separating precipitate by centrifugation, adding acetic acid into wet precipitate, and stirring for 1 hr. The molar ratio of acetic acid to Fe was 3: 1. Then 1g of mesoporous silica MCM-48 is added into the colloidal solution and stirred, so that colloidal particles are adsorbed on the surface of the carrier. The other catalyst preparation process was the same as catalyst 1 to obtain 40% FeHAc/MCM-48 catalyst (catalyst 15). The active component Fe of the catalyst is measured2O3The particle size was 3.2 nm. The particle size distribution range is 2.2-4.2 nm.
Example 16
4.81g of Fe (NO)3)3·9H2O is dissolved in 40ml of deionized water, stirred for 10min and then slowly added with 24ml of NaOH (1.18 mol. L)-1) Solution to obtain Fe (OH)xPrecipitating, separating precipitate by centrifugation, adding acetic acid into wet precipitate, and stirring for 1 hr. The molar ratio of acetic acid to Fe was 3: 1. Then, 1g of diatomaceous earth was added to the colloidal solution and stirred to adsorb the colloidal particles to the surface of the carrier. The other catalysts were prepared as described for catalyst 1 to yield 40% FeHAc/Diato catalyst (catalyst 16). The active component Fe of the catalyst is measured2O3The particle size was 4.5 nm. The particle size distribution range is 3.3-5.1 nm.
Example 17
4.81g of Fe (NO)3)3·9H2O is dissolved in 40ml of deionized water, stirred for 10min and then slowly added with 24ml of NaOH (1.18 mol. L)-1) Solution to obtain Fe (OH)xPrecipitating, separating precipitate by centrifugation, adding acetic acid into wet precipitate, and stirring for 1 hr. The molar ratio of acetic acid to Fe was 3: 1. Then, 1g of molecular sieve 13X was added to the colloidal solution and stirred to adsorb the colloidal particles to the surface of the carrier. The other catalysts were prepared as described for catalyst 1 to give 40% FeHAc/13X catalyst (catalyst 17). The active component Fe of the catalyst is measured2O3The particle size was 3.9 nm. The particle size distribution range is 2.8-4.7 nm.
Example 18
4.81g of Fe (NO)3)3·9H2O is dissolved in 40ml of deionized water, stirred for 10min and then slowly added with 24ml of NaOH (1.18 mol. L)-1) Solution to obtain Fe (OH)xPrecipitating, separating precipitate by centrifugation, adding acetic acid into wet precipitate, and stirring for 1 hr. The molar ratio of acetic acid to Fe was 3: 1. Then, 1g of molecular sieve Y is added into the colloidal solution and stirred, so that colloidal particles are adsorbed on the surface of the carrier. The other catalysts were prepared as described for catalyst 1 to give 40% FeHAc/Y catalyst (catalyst 18). The active component Fe of the catalyst is measured2O3The particle size was 5.1 nm. The particle size distribution range is 4.3-7.0 nm.
Example 19
0.112g of MnCl2·4H2O is dissolved in 10ml of deionized water, stirred for 10min and then slowly added with 1.9ml of NaOH (1.18 mol. L)-1) Solution to obtain Mn (OH)xPrecipitating, separating precipitate by centrifugation, adding acetic acid (the molar ratio of acetic acid to Mn is 3:1) into wet precipitate, and stirring for 1h until a hydrous manganese oxide colloidal solution is formed. Thereafter, 1g of catalyst 5 (40% FeHAc/SiO)2) As a carrier, the colloidal particles are added to the colloidal solution and stirred to adsorb the colloidal particles to the surface of the carrier. Other preparation processes are the same as the catalyst 1 to obtain Mn5Fe40/SiO2Catalyst (catalyst 19). TEM image showed that the average particle size of the supported particles was 4.2nm, particle sizeThe distribution range is 3.1-5.1 nm.
Example 20
0.22g of MnCl2·4H2O is dissolved in 20ml deionized water, stirred for 10min, and then 3.8ml NaOH (1.18 mol. L) is slowly added-1) Solution to obtain Mn (OH)xPrecipitating, separating precipitate by centrifugation, adding acetic acid (the molar ratio of acetic acid to Mn is 3:1) into wet precipitate, and stirring for 1h until a hydrous manganese oxide colloidal solution is formed. Thereafter, 1g of catalyst 5 (40% FeHAc/SiO)2) As a carrier, the colloidal particles are added to the colloidal solution and stirred to adsorb the colloidal particles to the surface of the carrier. The preparation process of other catalysts is the same as that of catalyst 1 to obtain Mn10Fe40/SiO2Catalyst (catalyst 20). TEM images show that the average particle size of the loaded particles is 4.7nm and the particle size distribution ranges from 3.9 to 6.0 nm.
Example 21
0.332g of MnCl2·4H2O is dissolved in 25ml deionized water, stirred for 10min, and then slowly added with 5.7ml NaOH (1.18 mol. L)-1) Solution to obtain Mn (OH)xPrecipitating, separating precipitate by centrifugation, adding acetic acid (the molar ratio of acetic acid to Mn is 3:1) into wet precipitate, and stirring for 1h until a hydrous manganese oxide colloidal solution is formed. Thereafter, 1g of catalyst 5 (40% FeHAc/SiO)2) As a carrier, the colloidal particles are added to the colloidal solution and stirred to adsorb the colloidal particles to the surface of the carrier. Other preparation processes are the same as the catalyst 1 to obtain Mn15Fe40/SiO2Catalyst (catalyst 21). The TEM image shows that the supported particles have an average particle size of 5.8nm and a particle size distribution in the range of 4.2-7.1 nm.
Example 22
0.246g of Co (NO)3)2·6H2O is dissolved in 10ml of deionized water, stirred for 10min and then slowly added with 1.9ml of NaOH (1.18 mol. L)-1) Solution to obtain Co (OH)xPrecipitating, separating precipitate by centrifugation, adding acetic acid (the molar ratio of the acetic acid to Co is 3:1) into wet precipitate, and stirring for 1h until a hydrated cobalt oxide colloidal solution is formed. Thereafter, 1g of catalyst 5 (40% FeHAc/SiO)2) Adding into the colloidal solution, stirring to make the colloidal particles adsorbed on the carrierThe surface of the body. Other preparation processes are the same as the catalyst 1 to obtain Co5Fe40/SiO2Catalyst (catalyst 22). The TEM image shows that the supported particles have an average particle size of 6.4nm and a particle size distribution in the range of 5.1-7.8 nm.
Example 23
0.112g of MnCl2·4H2O is dissolved in 10ml of deionized water, stirred for 10min and then 1g of catalyst 5 (40% FeHAc/SiO) is added2) Stirring for 30min, evaporating to dryness in 50 deg.C constant temperature water bath, drying at 60 deg.C for 6 hr, and calcining at 450 deg.C for 4 hr to obtain 5% Mn/40% FeHAc/SiO2Catalyst (catalyst 23). The TEM image shows that the supported particles have an average particle size of 5.5nm and a particle size distribution in the range of 4.8-6.6 nm.
Example 24
0.246g of Co (NO)3)2·6H2O is dissolved in 10ml of deionized water, stirred for 10min and then 1g of catalyst 5 (40% FeHAc/SiO) is added2) Stirring for 30min, evaporating to dryness in 50 deg.C constant temperature water bath, drying at 60 deg.C for 6 hr, and calcining at 450 deg.C for 4 hr to obtain 5% Co/40% FeHAc/SiO2Catalyst (catalyst 24). TEM images show that the supported particles have an average particle size of 6.2nm and a particle size distribution in the range of 5.0-7.9 nm.
Example 25
0.235g of Zr (NO)3)4·5H2O is dissolved in 10ml of deionized water, stirred for 10min and then 1g of catalyst 5 (40% FeHAc/SiO) is added2) Stirring for 30min, evaporating to dryness in a 50 deg.C constant temperature water bath, drying at 60 deg.C for 6 hr, and calcining at 450 deg.C for 4 hr to obtain 5% Zr/40% FeHAc/SiO2Catalyst (catalyst 25). TEM images show that the supported particles have an average particle size of 7.5nm and a particle size distribution in the range of 6.3-9.0 nm.
Example 26
0.417g of MgCl2·6H2O is dissolved in 10ml of deionized water, stirred for 10min and then 1g of catalyst 5 (40% FeHAc/SiO) is added2) Stirring for 30min, evaporating to dryness in 50 deg.C constant temperature water bath, drying at 60 deg.C for 6 hr, and calcining at 450 deg.C for 4 hr to obtain 5% Mg/40% FeHAc/SiO2Catalyst (catalyst 26). The TEM image shows that the supported particles have an average particle size of 6.8nm and a particle size distribution in the range of 4.9-7.5 nm.
Example 27
0.295g of Ca (NO)3)2·4H2O is dissolved in 10ml of deionized water, stirred for 10min and then 1g of catalyst 5 (40% FeHAc/SiO) is added2) Stirring for 30min, evaporating to dryness in 50 deg.C constant temperature water bath, drying at 60 deg.C for 6 hr, and calcining at 450 deg.C for 4 hr to obtain 5% Ca/40% FeHAc/SiO2Catalyst (catalyst 27). The TEM image shows that the average particle size of the loaded particles is 8.1nm and the particle size distribution range is 7.2-10.1 nm.
Example 28
4.81g of Fe (NO)3)3·9H2O is dissolved in 40ml of deionized water, stirred for 10min and then slowly added with 24ml of NaOH (1.18 mol. L)-1) Solution to obtain Fe (OH)xPrecipitating, separating precipitate by centrifugation, adding acetic acid (molar ratio of acetic acid to Fe is 3:1) into wet precipitate, and stirring for 1h until a hydrated iron oxide colloidal solution is formed. Then, 1g of porous silica gel was added to the colloidal solution and stirred to adsorb colloidal particles onto the surface of the carrier. Centrifuged and washed with pure water. After drying, roasting for 4h at 600 ℃ in air to obtain 40% FeHAc/SiO2600 catalyst (catalyst 28). TEM image showing Fe2O3The average particle diameter is 8.1nm, and the particle diameter distribution range is 7.3-9.6 nm.
Example 29
4.81g of Fe (NO)3)3·9H2O is dissolved in 40ml of deionized water, stirred for 10min and then slowly added with 24ml of NaOH (1.18 mol. L)-1) Solution to obtain Fe (OH)xPrecipitating, separating precipitate by centrifugation, adding acetic acid (molar ratio of acetic acid to Fe is 3:1) into wet precipitate, and stirring for 1h until a hydrated iron oxide colloidal solution is formed. Then, 1g of porous silica gel was slowly added to the colloidal solution and stirred to adsorb colloidal particles onto the surface of the carrier. Centrifuged and washed with pure water. After drying, roasting for 4h at 300 ℃ in air to obtain 40% FeHAc/SiO2300 catalyst (catalyst 29). TEM image showing Fe2O3The average particle size is 6.2nm, and the particle size distribution range is 5.1-7.5 nm.
Example 30
0.130g of KNO3Dissolved in 10ml of deionized water, stirred for 10min, and then 1g of catalyst 5 (40% FeHAc/SiO) was added2) Stirring for 30min, evaporating to dryness in 50 deg.C constant temperature water bath, drying at 60 deg.C for 6 hr, and calcining at 450 deg.C for 4 hr to obtain 5% K/40% FeHAc/SiO2Catalyst (catalyst 30). TEM images show that the average particle size of the loaded particles is 4.2nm and the particle size distribution ranges from 3.1 to 5.0 nm.
Example 31
0.185g of NaNO3Dissolved in 10ml of deionized water, stirred for 10min, and then 1g of catalyst 5 (40% FeHAc/SiO) was added2) Stirring for 30min, evaporating to dryness in 50 deg.C constant temperature water bath, drying at 60 deg.C for 6 hr, and calcining at 450 deg.C for 4 hr to obtain 5% Na/40% FeHAc/SiO2Catalyst (catalyst 31). The TEM image shows that the supported particles have an average particle size of 4.4nm and a particle size distribution in the range of 3.5-5.2 nm.
Example 32
1.80g of Fe (NO)3)3·9H2Dissolving O in 20ml deionized water, stirring for 10min, slowly adding 12ml NaOH (1.18 mol. L)-1) Solution to obtain Fe (OH)xPrecipitating, separating precipitate by centrifugation, adding acetic acid (molar ratio of acetic acid to Fe is 3:1) into wet precipitate, and stirring for 1h until a hydrated iron oxide colloidal solution is formed. Then 1g of catalyst 1 (20% FeHAc/SiO)2) As a carrier, the colloidal particles are added to the colloidal solution and stirred to adsorb the colloidal particles to the surface of the carrier. The other preparation processes are the same as the catalyst 1 to obtain 20 percent of Fe/20 percent of FeHAC/SiO2Catalyst (catalyst 32) and Fe content thereof was measured2O3The actual loading was 25.6%. TEM image showing Fe2O3The average particle diameter is 7.9nm, and the particle diameter distribution range is 6.4-9.2 nm.
Example 33
0.235g of Zr (NO)3)4·5H2O is dissolved in 10ml of deionized water, stirred for 10min, and then 1g of catalyst 23 (20% Fe/20%)FeHAC/SiO2) Stirring for 30min, evaporating to dryness in a 50 deg.C constant temperature water bath, drying at 60 deg.C for 6 hr, and calcining at 450 deg.C for 4 hr to obtain 5% Zr/20% Fe/20% FeHAC/SiO2Catalyst (catalyst 33). The TEM image shows that the supported particles have an average particle size of 10.5nm and a particle size distribution in the range of 7.3-14.5 nm.
Examples of the use of catalysts in FTO reactions
The catalytic performance of the catalyst on the Fischer-Tropsch synthesis reaction is evaluated by using a fixed bed continuous flow reactor. The quartz reactor had an inner diameter of 9mm and was diluted with 200mg of the catalyst and 200mg of quartz sand of the same particle size for each evaluation. The evaluation conditions were: the pressure is 2Mpa, the temperature is 300 ℃, the molar composition of reaction gas is CO: h2：N220:20: 5. Unless otherwise stated, the catalyst was at atmospheric pressure, H, before the evaluation experiment2Reducing in situ for 5h at 400 ℃ in the atmosphere, and switching to the reaction atmosphere after the reduction is finished. Part of the catalyst is reduced at 400 ℃ in a CO atmosphere, the catalyst name is appended with-CO to distinguish, e.g. 40% FeHAc/SiO2-CO. In addition, the effect of different reduction temperatures on the activity was also tested, e.g.40% FeHAc/SiO2Reducing in hydrogen at 300 deg.C and 600 deg.C respectively, and naming the catalyst as 40% FeHAc/SiO2R300 and 40% FeHAc/SiO2-R600. The results of the catalyst performance evaluation are shown in Table 1.
40% FeHAc/SiO prepared by comparative adsorption method2And 30% Fe/SiO prepared by dipping method2Imp, the actual loading of both being close (Fe)2O3Both the contents are 30%), the conversion rate of CO and the initial selectivity of the low-carbon olefin are obviously better than those of the former after 12 hours of reaction (attached table 1). The initial CO conversion rate of the former is 46.4 percent, and the conversion rate is stably maintained between 46 percent and 50 percent within 100 hours; while the latter had an initial CO conversion of 43.0% with the conversion continuing to drop to about 17.5% by 100 hours (fig. 19). Other silica-based materials are used as carriers, for example, mesoporous silica (SBA-15, KIT-6, MCM-41 and MCM-48), fibrous nano-silica KCC-1, molecular sieves (Beta, ZSM-5, 13X, Y), silica nanospheres (SiO. RTM. SiO. nanospheres)2NP), the catalyst obtainedAlso has FTO catalytic properties (table 1). Wherein after the 40% FeHAc/KCC-1 catalyst reacts for 12 hours, the CO conversion rate reaches 65.2%, and the selectivity of the low-carbon olefin reaches 18.6%.
In addition, the use of auxiliary metal (such as Mn, Mg, Co, Zr, Ca, K, Na) for modification can improve the selectivity of low carbon olefin although it may cause a certain reduction in CO conversion (Table 1).
TABLE 1 FTO catalytic Performance of the catalyst after 12h reaction
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (10)
1. A preparation method of a supported nano iron-based catalyst is characterized by comprising the following preparation steps:
(1) reacting ferric salt with alkali in water solution to obtain ferric hydroxide precipitate, filtering or centrifuging, adding acetic acid into the wet precipitate, and stirring to form ferric oxide hydrate colloidal solution;
(2) adding a silica-based carrier into the hydrated ferric oxide colloidal solution prepared in the step (1), and stirring to enable colloidal particles to be adsorbed on the surface of the carrier;
(3) after separating the solid and the liquid in the step (2), washing the solid with pure water, and drying and roasting to obtain the supported nano iron-based catalyst;
(4) and (3) taking the supported nano iron-based catalyst obtained in the step (3) as a carrier, and repeating the steps (1), (2) and (3) for 0 or more times to obtain the supported nano iron-based catalyst with higher loading capacity.
2. The method of claim 1, wherein the silica-based support comprises porous silica gel, mesoporous silica, fibrous nano-silica, diatomaceous earth, silica nanospheres, molecular sieves; the roasting temperature is 300-600 ℃; the reduction temperature is 300-600 ℃.
3. A preparation method of an assistant metal modified load type nanometer iron-based catalyst is characterized by comprising the following preparation steps:
(1) reacting ferric salt with alkali in water solution to obtain ferric hydroxide precipitate, filtering or centrifuging, adding acetic acid into the wet precipitate, and stirring to form ferric oxide hydrate colloidal solution;
(2) preparing a hydrated oxide colloidal solution of the auxiliary metal M by the same method in the step (1);
(3) adding a silica-based carrier into the hydrated ferric oxide colloidal solution prepared in the step (1), and stirring to enable colloidal particles to be adsorbed on the surface of the carrier;
(4) after separating the solid and the liquid in the step (3), washing the solid with pure water, and drying and roasting to obtain supported nano iron oxide;
(5) taking the loaded nano ferric oxide obtained in the step (4) as a carrier, and repeating the steps (1), (3) and (4) for 0 or more times to obtain the loaded nano ferric oxide with higher loading capacity;
(6) and (3) adding the supported nano iron oxide obtained in the step (4) or (5) as a carrier into the hydrated oxide colloidal solution of the assistant metal M obtained in the step (2), stirring to enable hydrated oxide colloidal particles of the metal M to be adsorbed on the surface of the carrier, separating solids, washing, drying and roasting to obtain the assistant metal M modified supported nano iron-based catalyst.
4. The method according to claim 3, wherein the promoter metal M is manganese or cobalt; and (3) when the metal M is cobalt, stirring in air after the cobalt hydroxide precipitate obtained in the step (2) is oxidized, filtering or centrifuging, adding acetic acid into the wet precipitate, and stirring until a hydrated cobalt oxide colloidal solution is formed.
5. The method of claim 3, wherein the silica-based support comprises porous silica gel, mesoporous silica, fibrous nano-silica, diatomaceous earth, silica nanospheres, molecular sieves; the roasting temperature is 300-600 ℃; the reduction temperature is 300-600 ℃.
6. A preparation method of an assistant metal modified load type nanometer iron-based catalyst is characterized by comprising the following preparation steps:
(1) reacting ferric salt with alkali in water solution to obtain ferric hydroxide precipitate, filtering or centrifuging, adding acetic acid into the wet precipitate, and stirring to form ferric oxide hydrate colloidal solution;
(2) adding a silica-based carrier into the hydrated ferric oxide colloidal solution prepared in the step (1), and stirring to enable colloidal particles to be adsorbed on the surface of the carrier;
(3) after separating the solid and the liquid in the step (2), washing the solid with pure water, and drying and roasting to obtain supported nano iron oxide;
(4) taking the loaded nano ferric oxide obtained in the step (3) as a carrier, and repeating the steps (1), (2) and (3) for 0 or more times to obtain the loaded nano ferric oxide with higher loading capacity;
(5) and (4) taking the supported nano iron oxide obtained in the step (3) or (4) as a carrier, dipping a salt solution of an auxiliary metal N onto the carrier, and drying and roasting to obtain the auxiliary metal N modified supported nano iron-based catalyst.
7. The method of claim 6, wherein the promoter metal N comprises zirconium, manganese, cobalt, magnesium, calcium, potassium, and sodium.
8. The method of claim 6, wherein the silica-based support comprises porous silica gel, mesoporous silica, fibrous nano-silica, diatomaceous earth, silica nanospheres, molecular sieves; the roasting temperature is 300-600 ℃; the reduction temperature is 300-600 ℃.
9. A supported nano iron-based catalyst, which is prepared by the method of any one of claims 1 to 2, the method of any one of claims 3 to 5, or the method of any one of claims 6 to 8.
10. The use of the supported nano iron-based catalyst of claim 9, wherein the supported nano iron oxide-based catalyst is reduced with carbon monoxide or hydrogen for the preparation of light olefins by fischer-tropsch synthesis.
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