CN105642355A - Crystalline polyacid complex-based composite Fischer-Tropsch catalyst and preparation method thereof - Google Patents

Crystalline polyacid complex-based composite Fischer-Tropsch catalyst and preparation method thereof Download PDF

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CN105642355A
CN105642355A CN201511004322.4A CN201511004322A CN105642355A CN 105642355 A CN105642355 A CN 105642355A CN 201511004322 A CN201511004322 A CN 201511004322A CN 105642355 A CN105642355 A CN 105642355A
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fischer
hpas
crystalline state
complex
tropsch catalysts
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李谦
王春玲
王兆龙
刘成
周国治
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
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Abstract

The invention relates to a crystalline polyacid complex-based composite Fischer-Tropsch catalyst and a preparation method thereof. The method is characterized in that the composite catalyst is prepared through compounding a crystalline polyacid complex to the surface of a Fischer-Tropsch catalyst in a solvent solving, dipping and in situ crystallization mode, and a mass ratio of the crystalline polyacid complex to the Fischer-Tropsch catalyst is 5-50:100. The composite catalyst has high C5-C12 target selectivity in a catalytic reaction, and can be used to directly produce gasoline and diesel oil components, so the technologic requirements are reduced, and the production cost is saved. The composite catalyst has the characteristics of high heat and structure stability, clear composition structure, and convenience for discussing the active site and researching the reaction mechanism. The preparation method has the advantages of simplicity, environmental protection, easy recycling and very good industrial application prospect.

Description

Compound fischer-tropsch catalysts based on crystalline state HPAs complex and preparation method thereof
Technical field
The present invention relates to a kind of fischer-tropsch catalysts and preparation method thereof, particularly class compound fischer-tropsch catalysts and preparation method thereof based on crystalline state HPAs complex.
Background technology
Polyoxometallate component is extensive, and structure change is various, has superpower acidity and good heat stability, is new and effective solid acid catalyst. There is the crystalline state HPAs complex of self supporting structure, resistance to water and high-ratio surface and not only have a large amount of abundant from one-dimensional to three-dimensional structure type, also there is the duct of multidimensional and higher specific surface area, and mostly be Hydrothermal Synthesis, there is good water resistant dissolubility. Crystalline state polyacid compound, as acid catalyst, has the advantage of himself uniqueness: 1) compound can determine structure by X-single crystal diffraction, this makes its Nomenclature Composition and Structure of Complexes clear and definite, it is simple to inquire into active center and research reaction mechanism; 2) polyoxoanion is as building block or counter ion counterionsl gegenions, is dispersed in the network of metal ion and organic ligand composition with molecular level form so that polyacid is evenly distributed, active sites distribution is homogeneous; 3) many acid molecules are combined with metal organic frame by covalent bond or hydrogen bond, such construct so that many acid molecules are firmly embedded in the middle of metallic organic framework, can keep Stability Analysis of Structures in catalytic process, it is to avoid the loss of polyacid component; 4) the internal pore passage structure existed of crystalline state polyacid compound, it is possible to realize the selective activization to reactant; 5) most importantly structure according to the requirement of catalytic reaction, can be carried out modulation by changing the compositing factors such as part, polyacid, metal cation by this catalyst, and design synthesis meets the crystalline state HPAs complex catalyst that different catalysis requires.
Being combined with traditional fischer-tropsch catalysts by crystalline state HPAs complex catalyst, fischer-tropsch catalysts site synthesis gas is converted into straight-chain hydrocarbons, and when straight-chain hydrocarbons is transferred to the acidic site of POMs, cracking and isomery form the hydrocarbon with side chain of low carbon number, thus realizing a step to prepare C5-C11, C12-C20The liquid fuel of section. The application of crystalline state polyacid compound is conducive to inquiring into active center, studies reaction mechanism.
Summary of the invention
An object of the present invention is to provide a class to be had and determines structure, is suitable for the compound fischer-tropsch catalysts based on crystalline state HPAs complex of Fischer-Tropsch synthesis.
The two of the purpose of the present invention are in that to provide the preparation method of this catalyst.
For reaching above-mentioned purpose, the present invention adopts the following technical scheme that
One class is based on the compound fischer-tropsch catalysts of crystalline state HPAs complex, it is characterised in that crystalline state HPAs complex is dissolved by this by solvent, the mode of dipping, in-situ crystallization, loads to fischer-tropsch catalysts surface and obtains composite catalyst; Wherein crystalline state HPAs complex with the mass ratio of fischer-tropsch catalysts is: 5%��50%.
Above-mentioned crystalline state HPAs complex is the polyacid coordination compound with zero dimension, one-dimensional, two-dimentional or three-dimensional discrete or support prolongation structure constructed by polyacid and metal organic fragment, and described polyacid is the polyacid of Keggin, Dawson, Anderson, Waugh or Lindqvist configuration; Described metal organic fragment is to be formed with nitrogenous pyridine or the part containing carboxylic acids by metal.
The formula of above-mentioned structure with Keggin polyacid is: Hn[XM12O40], wherein X is Si, Ge, P, As or B, and M is W or Mo, n=0��5; The one-tenth formula of described Dawson structure polyacid is: Hn[X2M18O62], wherein X to be P or As, M be=W or Mo, n=0��6; The composition formula of described Anderson structure polyacid is: [XM6O24]n-, wherein X is Al3+��Ga3+��Te6+��I7+; The composition formula of described Waugh structure polyacid is: X6[MnMo9O32], wherein X is NH4, K, Ba or Na; The composition formula of described Lindqvist structure polyacid is: Hn[XxMyO19], X&M is V, Nb, W, Mo or Ta, x+y=6, n=0��2.
Above-mentioned metal base metal, alkaline-earth metal, transition metal, rare earth metal or noble metal.
Above-mentioned alkali metal is draw together at least one in Li, Na, K and Cs; Described alkaline-earth metal is at least one in Mg, Ca and Ba; Described transition metal is at least one in Ti, Cr, Mn, Fe, Co, Ni, Cu and Zn; Described rare earth metal is: at least one in La, Ce, Pr, Nd, Sm and Eu; Described noble metal is at least one in Pd, Pt and Ru.
Above-mentioned nitrogenous pyridine is have the nitrogenous pyridine of rigid structure or have the nitrogenous pyridine of flexible structure; Described is have the part containing carboxylic acids of rigid structure or have the part containing carboxylic acids of flexible structure containing carboxylic acids part.
The above-mentioned nitrogenous pyridine with rigid structure is: 4,4'-bipyridyl, 2,5-bis-(3-pyridine)-1,3,4 oxadiazoles or 2,5-bis-(4-pyridine)-1,3,4 oxadiazoles; The described nitrogenous pyridine with flexible structure is: 2,2'-bipyridyl or 1,10-Phen; The described part containing carboxylic acids with rigid structure is: trimesic acid or p-phthalic acid; The described part containing carboxylic acids with flexible structure is phthalic acid.
Active metal cobalt, ferrum in above-mentioned fischer-tropsch catalysts, the content of ruthenium is 0.5��40 weight %; The content of oxide carrier is 40��97 weight %.
A kind of prepare the above-mentioned compound fischer-tropsch catalysts based on crystalline state HPAs complex, it is characterised in that concretely comprising the following steps of the method:
A. crystalline state HPAs complex is dissolved in water or organic solvent, incipient impregnation is in fischer-tropsch catalysts, the weight ratio of described crystalline state HPAs complex and fischer-tropsch catalysts is (5��50): 100, it is sufficiently stirred for 2-6 hour, in politef reactor, when hydro-thermal self-generated pressure, 100��200 DEG C of scopes, heating 24��120 hours, in-situ crystallization compound obtains composite catalyst;
B. step a gained composite catalyst being carried out roasting reduction, the recovery time is 2��6 hours, and reduction temperature is 100��300 degree, and reducing atmosphere is hydrogen, and then concentration 5��100% be passivated again, and atmosphere is O2/ Ar or O2/N2, the time is 10 minutes to 24 hours, prepares the compound fischer-tropsch catalysts based on crystalline state HPAs complex.
Above-mentioned solvent is: water, methanol, ethanol, N,N-dimethylformamide (DMF), N, N-diethylformamide (DEF), ether, acetonitrile or DMSO.
The first aspect of the invention there is provided the composite catalyst of a kind of HPAs complex compound fischer-tropsch synthetic catalyst with clear and definite structure, and this catalyst is applicable to Fischer-Tropsch fixed bed reactors. This composite catalyst comprises the crystalline state HPAs complex catalyst that mass fraction is 5-50%, comprises the fischer-tropsch synthetic catalyst that mass fraction is 50-95%. Involved polyoxometallate includes Keggin-type, Dawson type and Lindqvist type polyacid; Involved fischer-tropsch catalysts (being as the criterion with fischer-tropsch catalysts total amount) comprises the cobalt oxide of 0.5-40 weight %, ferrum oxide or ruthenium, 60-99.5 weight % oxide carrier.
The preparation method that second aspect of the present invention provides composite catalyst.
Specifically include following steps:
The first step: by the polyacid of the structure types such as Keggin or the combination of several structure polyacid, transition metal, organic ligand at room temperature, cultivate monocrystalline when hydrothermal/solvent heat, obtain monocrystalline state crystal structure;
Second step: prepare fischer-tropsch synthetic catalyst by the method for dipping, and catalyst is carried out roasting, reduction, passivation;
3rd step: by above-mentioned have determine that the HPAs complex catalyst of mono-crystalline structures is dissolved in the middle of water or organic solvent, incipient impregnation is in fischer-tropsch catalysts, it is 1:99-90:1 with fischer-tropsch catalysts according to weight ratio, is sufficiently stirred for 2-6 hour, in politef reactor, when hydro-thermal self-generated pressure, 100-200 DEG C of scope, heats 24-120 hour, dry, roasting, obtains composite catalyst.
The invention provides the composite catalyst based on crystalline state HPAs complex and fischer-tropsch catalysts and two kinds of preparation methoies preparing composite catalyst, have the advantage that
1. composite catalyst provided by the invention C in catalytic reaction5-C12Target selectivity high, it is possible to directly preparing gasoline, diesel component, thus reducing technological requirement, saving production cost.
2. composite catalyst provided by the invention has heat stability and the high feature of structural stability, and it is clear and definite to form structure, it is simple to inquire into active center, studies reaction mechanism.
3. the preparation method of composite catalyst provided by the invention is simple, environmental friendliness and being easily recycled, and has good prospects for commercial application.
Accompanying drawing explanation
Fig. 1 is the crystallographic structural analysis figure of the catalyst of the present invention;
The SEM scanning electron microscope (SEM) photograph of the catalyst that Fig. 2 is the present invention;
The in-situ crystallization of the catalyst that Fig. 3 is the present invention is to the SEM scanning electron microscope (SEM) photograph of fischer-tropsch catalysts;
The XRD structural characterization figure of the crystallization rear catalyst of the catalyst that Fig. 4 is the present invention.
Detailed description of the invention
Specifically list the preferred embodiment of the present invention in the examples below, but it is to be understood that protection scope of the present invention is not limited only to this.
The catalyst carrier used in following example is commercially available; The water used is deionized water; The slaine reagent used is commercially available analytical reagent, does not directly use after further treatment.
The preparation of the crystalline state HPAs complex that the present invention uses is referring to as follows:
1. Chemistry of Polyacids Chen Wei woods king grace ripple writes 2013 Science Presses
2. more than acidic group functional complexes Wang Xiuli Tian Aixiang writes 2014 Chemical Industry Press
Embodiment 1: determine composite catalyst composition and weight ratio listed by table 1 below.Crystalline state HPAs complex molecular formula is H11{Pd2(2,2?-bpy)2Cl2}2{Pd2(2,2?-bpy)O2Cl2}[PW12O40] (2,2-bpy=2,2-bipyridyl), by PdCl2, H3PW12O40With 2,2-bpy 160oReacting acquisition in 5 days under C hydrothermal condition, crystallographic data is as follows: Monoclinic, P2 (1)/c, a=11.060 (12), b=25.802 (3), c=22.353 (2), ��=91.146 (2) ��, Z=4. Single crystal X-ray diffraction research is shown to be by a Keggin-type polyanionic [PW12O40]3-With the supramolecular structure with one-dimensional channels that Pd coordination polymer is combined together to form by hydrogen bond action, Pd ion is the plane quadrilateral configuration of four-coordination.
By 0.2 gram of HPAs complex catalyst C10H10Cl3N2O40PdPW12O40It is dissolved in 2ml acetonitrile, incipient impregnation to 0.8 gram fischer-tropsch catalysts 10Co/Al2O3In. Under 160 DEG C of conditions, crystallization obtained composite catalyst after 4 hours. This composite catalyst is placed in pipe reaction stove and uses 10%H2/N2Reducing, heating rate is 1 DEG C/min, and reduction temperature is 300 DEG C, and the recovery time is 2 hours, and the catalyst after reduction is slowly cooled to room temperature, keeps above-mentioned gaseous mixture in cooling procedure, after then purging 20 minutes with nitrogen, uses 1%O2/N2Gaseous mixture is passivated 1 hour, then sealed storage. By the catalyst called after CF-1 of above-mentioned preparation.
Embodiment 2: determine composite catalyst composition and weight ratio listed by table 1 below. Crystalline state HPAs complex molecular formula is H8{Pd(2,2-bpy)Cl}6{Pd(2,2-bpy)Cl2}[P2W18O62] (2,2-bpy=2,2-bipyridyl), by PdCl2, K6P2W18O62With 2,2-bpy 130oReacting acquisition in 3 days under C hydrothermal condition, crystallographic data is as follows: Monoclinic, P2 (1)/m, a=15.368 (14), b=17.964 (16), c=22.186 (2), ��=107.840 (2) ��, Z=2. Single crystal X-ray diffraction is shown to be by a Dawson type anion [P2W18O62]6-With the supramolecular structure with one-dimensional channels that Pd coordination polymer is combined by hydrogen bond and �� key effect, Pd ion is the plane quadrilateral configuration of four-coordination.
By 0.1 gram of above-mentioned HPAs complex catalyst dissolution in 2ml ethanol, magnetic agitation 30 minutes is to being completely dissolved. By 0.9 gram of fischer-tropsch catalysts 10Co/Al2O3Putting in beaker, mechanical agitation, to the solution impregnation containing polyacid in the middle of fischer-tropsch catalysts carrier duct. Keeping dipping 6 hours, period stirred once every half an hour, it is ensured that be sufficiently impregnated with. Then being transferred to by the catalyst in beaker in the autoclave of 25ml polytetrafluoroethylliner liner, 130 DEG C of heating temperatures 72 hours, Temperature fall, take out dry after cooling, 200 DEG C of roastings obtain composite catalyst in 4 hours. This composite catalyst is placed in pipe reaction stove and uses 3%H2/N2Reducing, heating rate is 2 DEG C/min, and reduction temperature is 200 DEG C, and the recovery time is 5 hours, and the catalyst after reduction is slowly cooled to room temperature, keeps above-mentioned gaseous mixture in cooling procedure, after then purging 1 hour with nitrogen, uses 5%O2/ Ar gaseous mixture is passivated 4 hours, then sealed storage. By the catalyst called after CF-2 of above-mentioned preparation.
Embodiment 3: determine composite catalyst composition and weight ratio listed by table 1 below. Crystalline state HPAs complex molecular formula is { Co (2,2-bpy)2}2[SiW12O40]2, by cobalt nitrate, H4SiW12O40With 2,2-bpy 180oAcquisition in 3 days is reacted under C hydrothermal condition. Single crystal X-ray diffraction research is shown to be by a Keggin-type polyanionic [SiW12O40]4-The two-dimension plane structure formed is combined by hydrogen bond action with Co coordination polymer.
By 0.4 gram of above-mentioned HPAs complex catalyst dissolution in 9ml methanol, incipient impregnation to 2 grams fischer-tropsch catalysts Ru/SiO2In.Under 180 DEG C of conditions, crystallization obtained composite catalyst after 48 hours. This composite catalyst is placed in pipe reaction stove and uses 10%H2/N2Reducing, heating rate is 1 DEG C/min, and reduction temperature is 300 DEG C, and the recovery time is 1 hour, and the catalyst after reduction is slowly cooled to room temperature, keeps above-mentioned gaseous mixture in cooling procedure, after then purging 20 minutes with nitrogen, uses 1%O2/N2Gaseous mixture is passivated 1 hour, then sealed storage. By the catalyst called after CF-3 of above-mentioned preparation.
Embodiment 4: determine composite catalyst composition and weight ratio listed by table 1 below. Crystalline state HPAs complex molecular formula is { Mn2(4-bpo)}3[P2W18O62], by Mn (NO3)2, H6P2W18O62With 4-bpo 160oAcquisition in 5 days is reacted under C hydrothermal condition. Single crystal X-ray diffraction research is shown to be by a Dawson type polyanionic [P2W18O62]6-The supramolecular structure formed is combined by covalent bond effect with Mn coordination polymer.
By 0.5 gram of above-mentioned HPAs complex catalyst dissolution in 5ml water, incipient impregnation to 1 gram fischer-tropsch catalysts Ru/TiO2In. Under 160 DEG C of conditions, crystallization obtained composite catalyst after 72 hours. This composite catalyst is placed in pipe reaction stove and uses 10%H2/N2Reducing, heating rate is 1 DEG C/min, and reduction temperature is 200 DEG C, and the recovery time is 2 hours, and the catalyst after reduction is slowly cooled to room temperature, keeps above-mentioned gaseous mixture in cooling procedure, after then purging 20 minutes with nitrogen, uses 1%O2/N2Gaseous mixture is passivated 4 hours, then sealed storage. By the catalyst called after CF-4 of above-mentioned preparation.
Embodiment 5: determine composite catalyst composition and weight ratio listed by table 1 below. Crystalline state HPAs complex molecular formula is { Cu (4,4-bpy)2}[BW12O40], by CuCl2, H5BW12O40With 4,4-bpy 150oAcquisition in 3 days is reacted under C hydrothermal condition. Single crystal X-ray diffraction research is shown to be by polyacid H5BW12O40With the three-dimensional porous structure that Cu coordination polymer passes through coordinate bond binding ability.
By 0.7 gram of above-mentioned HPAs complex catalyst dissolution in 7ml solvent DMF, incipient impregnation to 1.3 grams fischer-tropsch catalysts 10Co/TiO2In. Under 180 DEG C of conditions, crystallization obtained composite catalyst after 48 hours. Being placed in pipe reaction stove by this composite catalyst to reduce with pure hydrogen, heating rate is 5 DEG C/min, and reduction temperature is 350 DEG C, recovery time is 1 hour, and the catalyst after reduction is slowly cooled to room temperature, keeps above-mentioned gaseous mixture in cooling procedure, then, after purging 20 minutes with nitrogen, 1%O is used2/N2Gaseous mixture is passivated 10 hours, then sealed storage. By the catalyst called after CF-5 of above-mentioned preparation.
Embodiment 6: determine composite catalyst composition and weight ratio listed by table 1 below. Crystalline state HPAs complex molecular formula is { Cu (3-bpo)2}[AlMo6O24], by CuCl2, [AlMo6O24]9-With 3-bpo 160oAcquisition in 3 days is reacted under C hydrothermal condition. Single crystal X-ray diffraction research is shown to be by [AlMo6O24] and the coordination polymer of three-dimensional porous structure that formed by covalent bond coordination of Cu ion.
By 0.4 gram of above-mentioned HPAs complex catalyst dissolution in 6mlDMSO, incipient impregnation to 0.6 gram fischer-tropsch catalysts 10Fe/Al2O3In. Under 160 DEG C of conditions, crystallization obtained composite catalyst after 30 hours. This composite catalyst is placed in pipe reaction stove and uses H2Reducing, heating rate is 5 DEG C/min, and reduction temperature is 300 DEG C, and the recovery time is 0.5 hour, and the catalyst after reduction is slowly cooled to room temperature, keeps above-mentioned gaseous mixture in cooling procedure, after then purging 60 minutes with nitrogen, uses 1%O2/N2Gaseous mixture is passivated 1 hour, then sealed storage.By the catalyst called after CF-6 of above-mentioned preparation.
Embodiment 7: determine composite catalyst composition and weight ratio listed by table 1 below. Crystalline state HPAs complex molecular formula is { Fe (4,4-bpy)2}[MnMo9O32], by FeCl3, [MnMo9O32] and 2,2-bpy 180oAcquisition in 3 days is reacted under C hydrothermal condition. Single crystal X-ray diffraction research is shown to be by [MnMo9O32] and Fe coordination polymer by what hydrogen bond action was combined together to form, there is one-dimensional catenary structure.
By 0.5 gram of above-mentioned HPAs complex catalyst dissolution in 5ml ethanol, incipient impregnation to 0.5 gram fischer-tropsch catalysts 20Fe/SiO2In. Under 180 DEG C of conditions, crystallization obtained composite catalyst after 24 hours. This composite catalyst is placed in pipe reaction stove and uses H2Reducing, heating rate is, 1 DEG C/min, and reduction temperature is 300 DEG C, and the recovery time is 1 hour, and the catalyst after reduction is slowly cooled to room temperature, keeps above-mentioned gaseous mixture in cooling procedure, after then purging 30 minutes with nitrogen, uses 1%O2/N2Gaseous mixture is passivated 1 hour, then sealed storage. By the catalyst called after CF-7 of above-mentioned preparation.
Embodiment 8: determine composite catalyst composition and weight ratio listed by table 1 below. Crystalline state HPAs complex molecular formula is { Zn (1,10-phen)2}[VW5O19], by ZnCl2, [VW5O19] and 1,10-phen 100oAcquisition in 3 days is reacted under C hydrothermal condition. Single crystal X-ray diffraction research is shown to be by [VW5O19] and the supramolecular structure that is combined together to form by hydrogen bond action of Zn coordination polymer.
By 0.1 gram of above-mentioned HPAs complex catalyst dissolution in 9ml acetonitrile, incipient impregnation to 0.9 gram fischer-tropsch catalysts 3Ru/Al2O3In. Under 100 DEG C of conditions, crystallization obtained composite catalyst after 36 hours. This composite catalyst is placed in pipe reaction stove and uses 10%H2/N2Reducing, heating rate is 1 DEG C/min, and reduction temperature is 300 DEG C, and the recovery time is 1 hour, and the catalyst after reduction is slowly cooled to room temperature, keeps above-mentioned gaseous mixture in cooling procedure, after then purging 30 minutes with nitrogen, uses 1%O2/N2Gaseous mixture is passivated 2 hours, then sealed storage. By the catalyst called after CF-8 of above-mentioned preparation.
Embodiment 9: determine composite catalyst composition and weight ratio listed by table 1 below. Crystalline state HPAs complex molecular formula is { La (4-bpo)2}[Mo6O19], by Lanthanum (III) nitrate, [Mo6O19] and 4-bpo 180oReact under C hydrothermal condition 2 days and obtain. Single crystal X-ray diffraction research is shown to be by [Mo6O19] and the supramolecular structure that is combined together to form by hydrogen bond action of La coordination polymer.
By 0.2 gram of above-mentioned HPAs complex catalyst dissolution in 8ml methanol, incipient impregnation to 0.8 gram fischer-tropsch catalysts 10Co/ZrO2In. Under 200 DEG C of conditions, crystallization obtained composite catalyst after 10 hours. This composite catalyst is placed in pipe reaction stove and uses 10%H2/N2Reducing, heating rate is 1 DEG C/min, and reduction temperature is 300 DEG C, and the recovery time is 2 hours, and the catalyst after reduction is slowly cooled to room temperature, keeps above-mentioned gaseous mixture in cooling procedure, after then purging 20 minutes with nitrogen, uses 1%O2/N2Gaseous mixture is passivated 1 hour, then sealed storage. By the catalyst called after CF-9 of above-mentioned preparation.
Embodiment 10: determine composite catalyst composition and weight ratio listed by table 1 below. Crystalline state HPAs complex molecular formula is { Ce (4,4-bpy)2}[PTi2W10O40], by cerous nitrate, [PTi2W10O40] and 4,4-bpy 150oAcquisition in 3 days is reacted under C hydrothermal condition.Single crystal X-ray diffraction research is shown to be by a Keggin-type polyanionic [PW12O40]3-The supramolecular structure with one-dimensional channels being combined together to form by hydrogen bond action with Pd coordination polymer.
By 0.4 gram of above-mentioned HPAs complex catalyst dissolution in 4mlDMF, incipient impregnation to 0.6 gram fischer-tropsch catalysts 3Ru/ZrO2In. Under 150 DEG C of conditions, crystallization obtained composite catalyst after 24 hours. This composite catalyst is placed in pipe reaction stove and uses 10%H2/N2Reducing, heating rate is 2 DEG C/min, and reduction temperature is 300 DEG C, and the recovery time is 2 hours, and the catalyst after reduction is slowly cooled to room temperature, keeps above-mentioned gaseous mixture in cooling procedure, after then purging 20 minutes with nitrogen, uses 1%O2/N2Gaseous mixture is passivated 1 hour, then sealed storage. By the catalyst called after CF-10 of above-mentioned preparation.
Embodiment 11: determine composite catalyst composition and weight ratio listed by table 1 below. Crystalline state HPAs complex molecular formula is { Mn (1,10-phen)2}3[P2W18O62], by MnCl2, [P2W18O62] and 1,10-phen 110oAcquisition in 7 days is reacted under C hydrothermal condition. Single crystal X-ray diffraction research is shown to be by [P2W18O62] and the supramolecular structure with one-dimensional channels that is combined together to form by hydrogen bond action of Mn coordination polymer.
By 0.3 gram of above-mentioned HPAs complex catalyst dissolution in 3ml water, incipient impregnation to 0.7 gram fischer-tropsch catalysts 10Co/SiO2In. Under 110 DEG C of conditions, crystallization obtained composite catalyst after 72 hours. This composite catalyst is placed in pipe reaction stove and uses 10%H2/N2Reducing, heating rate is 1 DEG C/min, and reduction temperature is 300 DEG C, and the recovery time is 2 hours, and the catalyst after reduction is slowly cooled to room temperature, keeps above-mentioned gaseous mixture in cooling procedure, after then purging 20 minutes with nitrogen, uses 1%O2/N2Gaseous mixture is passivated 1 hour, then sealed storage. By the catalyst called after CF-11 of above-mentioned preparation.
Embodiment 12: determine composite catalyst composition and weight ratio listed by table 1 below. Crystalline state HPAs complex molecular formula is { Zn (3-bpo)2}[V2W4O19], by ZnCl2, [V2W4O19] and 3-bpo 170oAcquisition in 5 days is reacted under C hydrothermal condition. Single crystal X-ray diffraction research is shown to be by [V2W4O19] and Zn ion, bpo forms the polyacid coordination polymer with three dimensional structure by covalent bond coordination.
By 0.5 gram of above-mentioned HPAs complex catalyst dissolution in 5ml methanol, incipient impregnation to 0.5 gram fischer-tropsch catalysts 20Fe/TiO2In. Under 170 DEG C of conditions, crystallization obtained composite catalyst after 48 hours. This composite catalyst is placed in pipe reaction stove and uses 10%H2/N2Reducing, heating rate is 1 DEG C/min, and reduction temperature is 300 DEG C, and the recovery time is 1 hour, and the catalyst after reduction is slowly cooled to room temperature, keeps above-mentioned gaseous mixture in cooling procedure, after then purging 60 minutes with nitrogen, uses 1%O2/N2Gaseous mixture is passivated 3 hours, then sealed storage. By the catalyst called after CF-12 of above-mentioned preparation.
From the data shown in upper table it will be seen that compared with the fischer-tropsch catalysts F without many acid catalysts, the composite catalyst of the present invention has notable C5-C12Selectivity.

Claims (10)

1. a class is based on the compound fischer-tropsch catalysts of crystalline state HPAs complex, it is characterised in that crystalline state HPAs complex is dissolved by this by solvent, the mode of dipping, in-situ crystallization, loads to fischer-tropsch catalysts surface and obtains composite catalyst; Wherein crystalline state HPAs complex with the mass ratio of fischer-tropsch catalysts is: 5%��50%.
2. the compound fischer-tropsch catalysts based on crystalline state HPAs complex according to claim 1, it is characterized in that described crystalline state HPAs complex is the polyacid coordination compound with zero dimension, one-dimensional, two-dimentional or three-dimensional discrete or support prolongation structure constructed by polyacid and metal organic fragment, described polyacid is the polyacid of Keggin, Dawson, Anderson, Waugh or Lindqvist configuration; Described metal organic fragment is to be formed with nitrogenous pyridine or the part containing carboxylic acids by metal.
3. the compound fischer-tropsch catalysts based on crystalline state HPAs complex according to claim 2, it is characterised in that the formula of described structure with Keggin polyacid is: Hn[XM12O40], wherein X is Si, Ge, P, As or B, and M is W or Mo, n=0��5; The one-tenth formula of described Dawson structure polyacid is: Hn[X2M18O62], wherein X to be P or As, M be=W or Mo, n=0��6; The composition formula of described Anderson structure polyacid is: [XM6O24]n-, wherein X is Al3+��Ga3+��Te6+��I7+; The composition formula of described Waugh structure polyacid is: X6[MnMo9O32], wherein X is NH4, K, Ba or Na; The composition formula of described Lindqvist structure polyacid is: Hn[XxMyO19], X&M is V, Nb, W, Mo or Ta, x+y=6, n=0��2.
4. the compound fischer-tropsch catalysts based on crystalline state HPAs complex according to claim 1, it is characterised in that described metal base metal, alkaline-earth metal, transition metal, rare earth metal or noble metal.
5. the compound fischer-tropsch catalysts based on crystalline state HPAs complex according to claim 4, it is characterised in that described alkali metal is draw together at least one in Li, Na, K and Cs; Described alkaline-earth metal is at least one in Mg, Ca and Ba; Described transition metal is at least one in Ti, Cr, Mn, Fe, Co, Ni, Cu and Zn; Described rare earth metal is: at least one in La, Ce, Pr, Nd, Sm and Eu; Described noble metal is at least one in Pd, Pt and Ru.
6. the compound fischer-tropsch catalysts based on crystalline state HPAs complex according to claim 1, it is characterised in that described nitrogenous pyridine is have the nitrogenous pyridine of rigid structure or have the nitrogenous pyridine of flexible structure; Described is have the part containing carboxylic acids of rigid structure or have the part containing carboxylic acids of flexible structure containing carboxylic acids part.
7. the compound fischer-tropsch catalysts based on crystalline state HPAs complex according to claim 6, it is characterized in that the described nitrogenous pyridine with rigid structure is: 4,4'-bipyridyl, 2,5-bis-(3-pyridine)-1,3,4 oxadiazoles or 2,5-bis-(4-pyridines)-1,3,4 oxadiazoles; The described nitrogenous pyridine with flexible structure is: 2,2'-bipyridyl or 1,10-Phen; The described part containing carboxylic acids with rigid structure is: trimesic acid or p-phthalic acid; The described part containing carboxylic acids with flexible structure is phthalic acid.
8. the compound fischer-tropsch catalysts based on crystalline state HPAs complex according to claim 1, it is characterised in that active metal cobalt, ferrum in described fischer-tropsch catalysts, the content of ruthenium is 0.5��40 weight %; The content of oxide carrier is 40��97 weight %.
9. the compound fischer-tropsch catalysts based on crystalline state HPAs complex prepared according to any one of claim 18, it is characterised in that concretely comprising the following steps of the method:
A. crystalline state HPAs complex is dissolved in water or organic solvent, incipient impregnation is in fischer-tropsch catalysts, the weight ratio of described crystalline state HPAs complex and fischer-tropsch catalysts is (5��50): 100, it is sufficiently stirred for 2-6 hour, in politef reactor, when hydro-thermal self-generated pressure, 100��200 DEG C of scopes, heating 24��120 hours, in-situ crystallization compound obtains composite catalyst;
B. step a gained composite catalyst being carried out roasting reduction, the recovery time is 2��6 hours, and reduction temperature is 100��300 degree, and reducing atmosphere is hydrogen, and then concentration 5��100% be passivated again, and atmosphere is O2/ Ar or O2/N2, the time is 10 minutes to 24 hours, prepares the compound fischer-tropsch catalysts based on crystalline state HPAs complex.
10. method according to claim 9, it is characterised in that described solvent is: water, methanol, ethanol, DMF (DMF), N, N-diethylformamide (DEF), ether, acetonitrile or DMSO.
CN201511004322.4A 2015-12-29 2015-12-29 Crystalline polyacid complex-based composite Fischer-Tropsch catalyst and preparation method thereof Pending CN105642355A (en)

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