CN114057209A - Zirconium-containing heteroatom molecular sieve, preparation method and application thereof - Google Patents

Zirconium-containing heteroatom molecular sieve, preparation method and application thereof Download PDF

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CN114057209A
CN114057209A CN202010748033.XA CN202010748033A CN114057209A CN 114057209 A CN114057209 A CN 114057209A CN 202010748033 A CN202010748033 A CN 202010748033A CN 114057209 A CN114057209 A CN 114057209A
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zirconium
molecular sieve
reaction
hydroxyl
molar ratio
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CN114057209B (en
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彭欣欣
林民
朱斌
夏长久
罗一斌
舒兴田
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/32—Oxygen atoms
    • C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
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    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention provides a zirconium-containing heteroatom molecular sieve, a preparation method and application thereof, wherein the molar ratio of zirconium to silicon at the surface part of the zirconium-containing heteroatom molecular sieve is higher than that of zirconium to silicon at the central part, and the molar ratio of zirconium to silicon in a molecular sieve body phase is (0.001-0.04): 1; the preparation method comprises the steps of contacting a molecular sieve N with skeleton hydroxyl vacancies with a polyhydroxy compound, processing and separating to obtain a molecular sieve O, contacting the molecular sieve O with a liquid P containing a zirconium source, and recovering a product; the molecular sieve is used for catalyzing MPV reaction, and has high catalytic activity, good product yield and difficult inactivation of an active center.

Description

Zirconium-containing heteroatom molecular sieve, preparation method and application thereof
Technical Field
The invention relates to a heteroatom molecular sieve, a preparation method and application thereof, and further relates to a zirconium-containing heteroatom molecular sieve, a preparation method and application thereof in the field of catalytic reduction reaction.
Background
The Zr-beta molecular sieve is a heteroatom molecular sieve with a molecular sieve framework with four coordinated Zr atoms and a BEA topological structure. The zirconium atoms of the framework are in Lewis acidity, and meanwhile, the beta molecular sieve has a three-dimensional twelve-membered ring pore channel structure, so that the beta molecular sieve can be suitable for catalytic reaction of larger molecules, and therefore, the Zr-beta molecular sieve is a Lewis acid catalytic material with excellent performance.
At present, Zr-beta can be used for activating hydrogen peroxide to catalyze the oxidation of organic substrates such as olefin, aromatic hydrocarbon, thioether and the like, catalyzing Baeyer-Villiger reaction, catalyzing esterification reaction, intramolecular hydrogen transfer reaction (glucose and fructose isomerization), aldol condensation reaction, diene addition reaction (Diels-Alder reaction), MPV (Meerwein-Ponndorf-Verley) reaction and the like, and has important function in the preparation of high-end fine chemicals.
The Zr-beta molecular sieve is mainly prepared by hydrothermal synthesis or silicon-aluminum beta molecular sieve post-treatment synthesis. The hydrothermal synthesis method needs to introduce fluorinion or add seed crystal, and the molecular sieve product is obtained through long-time crystallization treatment. The introduction of fluoride ions makes wastewater treatment difficult. Moreover, the crystal grain size of the Zr-beta molecular sieve obtained by adopting a fluorine ion system or adding seed crystals for synthesis is generally larger and reaches about micron level (Catal. Sci. Technol.,2016,6, 3018-type 3026).
Yongzhong Zhu et al (CHEM. COMMON., 2003, p 2734-2735) use TEOS (tetraethyl silicate) as the silicon source, TEAOH (tetraethylammonium hydroxide) as the alkali source and templating agent, ZrOCl2·8H2O is a zirconium source, HF (hydrofluoric acid) aqueous solution is a mineralizer, and simultaneously, dealuminated beta molecular sieve is added as a seed crystal, and the Zr-beta molecular sieve is obtained by hydrothermal crystallization treatment at 140-170 ℃ for 5-30 days. The Zr-beta molecular sieve prepared by the method has low conversion rate in MPV reaction for larger molecules (Journal of Catalysis 227(2004) 1-10). The Zr-beta molecular sieve prepared by the hydro-thermal synthesis method also has the defects of short service life and easy inactivation in the MPV reaction (Catal. Sci. Technol., 2016),6,3018–3026)。
The Zr-beta molecular sieve synthesized by adopting the silicon-aluminum beta molecular sieve after-treatment does not need crystallization, does not use fluorine-containing compounds and organic templates, and has simple and efficient preparation process, thereby being concerned.
Gang Li et al (ACS Sustainable chem. Eng.2018,6,4316-4320) used 7.2MHNO3(55mL per gram of molecular sieve) after treating the Si-Al beta molecular sieve at 80 ℃ for 4h to remove aluminum, dissolving Zr (NO)3)4·5H2Treating the ethanol solution of O to insert zirconium atoms, drying and roasting the solid powder of O, and treating the solid powder with a sodium hydroxide solution to obtain the Zr-beta molecular sieve; when the Zr-beta molecular sieve is used in the MPV reaction of furfural derivatives, the conversion rate of raw materials and the yield of target products are low.
Bo Tang et al (Green chem.,2015,17,1744) use oxalic acid solution to treat silicon-aluminum beta molecular sieve for partial dealumination, then use alkali to treat and expand pores, then use 13mol/L nitric acid solution to perform dealumination for 20h to obtain full-silicon beta molecular sieve rich in mesopores, and finally use it and zirconium source zirconocene dichloride (Cp2 ZrCl)2) And grinding in a glove box, and roasting to obtain the mesoporous Zr-beta molecular sieve. The molecular sieve shows good activity in the reaction of macromolecular amine and epoxide, but the preparation process of the catalyst is too complex.
The Zr-beta molecular sieve directly synthesized by hydro-thermal method has more uniform distribution of zirconium species, but the problems of hole blocking, inactivation and the like are easily caused because the crystal grains of the molecular sieve are larger and the diffusion resistance of compound molecules in the molecular sieve is large. The Zr-beta molecular sieve is prepared by post-synthesis, and the prepared Zr-beta molecular sieve has the problems of low activity, short service life and the like due to the distribution of aluminum species of a parent silicon-aluminum-beta molecular sieve. Although the problem can be alleviated by preparing the mesoporous Zr-beta molecular sieve through post-treatment, the preparation process is complex and difficult to apply on a large scale. In conclusion, a new type of Zr-beta molecular sieve is urgently needed to be developed to solve the problems of low molecular sieve activity and short service life caused by large diffusion resistance of molecules in the existing Zr-beta molecular sieve.
Disclosure of Invention
The invention aims to provide a zirconium-containing heteroatom molecular sieve to solve the problems of low activity, short service life, complex preparation method and the like of the conventional zirconium-containing molecular sieve in the application process, and the invention aims to provide a simple and convenient preparation method. The invention also aims to provide an application of the molecular sieve.
In order to achieve one of the purposes of the invention, the molar ratio of zirconium to silicon at the surface part of the molecular sieve is higher than that at the central part, and the molar ratio of zirconium to silicon in the molecular sieve bulk phase is (0.001-0.04): 1; the molar ratio of zirconium to silicon at the surface part of the molecular sieve and the molar ratio of zirconium to silicon at the central part of the molecular sieve are both characterized and measured by a TEM energy spectrum, and a rectangular selected area at the surface part of the molecular sieve and a rectangular selected area at the central part of the molecular sieve of a TEM morphology picture of a molecular sieve crystal grain are respectively selected as target spots for composition analysis; wherein the content of the first and second substances,
the rectangular selection area on the surface of the molecular sieve is characterized in that a tangent is made at the boundary of the molecular sieve crystal grain, an area which is perpendicular to the tangent and has a distance of less than 10nm is selected, the rectangular selection area is located in the area, and the overlapping area of the rectangular selection area and the molecular sieve crystal grain is 50-3000 nm2；
The rectangular selection area at the central part of the molecular sieve takes the grain boundary of the molecular sieve as a minimum inscribed circle and takes 50 percent of the radius of the inscribed circle as a concentric circle, the rectangular selection area falls in the concentric circle, and the area of the rectangular selection area is 50-3000 nm2。
When the molecular sieve is measured by using TEM spectral characterization, rectangular selection areas with the same area are selected at the surface part and the central part.
In the invention, the molar ratio of zirconium to silicon at the surface part of the molecular sieve is higher than that at the central part, and the molar ratio of zirconium to silicon in the molecular sieve phase is (0.001-0.04): 1. preferably (0.005-0.02):1, more preferably (0.008-0.015): 1.
In the invention, the zirconium element in the molecular sieve is mainly enriched on the surface of the molecular sieve. The TEM energy spectrum is used for characterization, and the ratio of the molar ratio of zirconium to silicon at the surface part of the molecular sieve to the molar ratio of zirconium to silicon at the central part of the molecular sieve can be (1.5-200): 1. preferably (5-100): 1, further preferably (10-70): 1. more preferably (20-50): 1.
in the present invention, the molecular sieve has a mesoporous or macroporous or mesoporous topology, preferably but not limited to BEA structure, MWW, CON, EWT, MSE, × -ITN, IFR, DON, CFI, UTL, OKO, etc. structures are also suitable for the type of molecular sieve of the present invention. The molecular sieve is not limited to the kind and content of elements, and besides zirconium element, the molecular sieve may also contain at least one element of aluminum, boron, titanium, tin, vanadium, cobalt, chromium, hafnium, tantalum, tungsten and lead, and the molar ratio of the element to silicon is (0-0.04): 1, preferably only zirconium is used as a heteroatom element.
In order to achieve the second object of the present invention, the present invention also provides a method for preparing the above-mentioned molecular sieve containing zirconium heteroatom, which is characterized in that the method comprises the steps of contacting molecular sieve N having skeletal hydroxyl vacancies with a polyhydroxy compound, treating and separating to obtain molecular sieve O, contacting molecular sieve O with a liquid P containing a zirconium source, and recovering the product.
In the preparation method provided by the invention, the molecular sieve N with skeleton hydroxyl vacancies can be obtained by direct synthesis such as a hydrothermal synthesis method, or can be obtained by post-treatment such as removing part of skeleton atoms, for example, removing part of skeleton atoms by acid treatment, alkali treatment, high-temperature hydrothermal treatment or microwave treatment and the like. Preferably by post-treatment. Preferably, the parent molecular sieve used in the post-treatment is a silicoaluminophosphate molecular sieve.
The skeleton hydroxyl vacancy refers to the infrared hydroxyl spectrogram of the skeleton hydroxyl vacancy with the wave number of 3550cm-1And a characteristic peak is obvious nearby. 3550cm in infrared hydroxyl spectrogram of the molecular sieve-1Nearby signal peaks can characterize the nest hydroxyl group, 3735cm-1The nearby signal peaks may characterize the terminal hydroxyl groups. The molecular sieve N is a silicon-aluminum molecular sieve, and an infrared hydroxyl spectrogram of the molecular sieve N is 3735cm after partial framework atoms are removed-1The intensity (in terms of peak height) and wave number of the near characteristic peak are 3550cm-1Ratio I of intensities (in terms of peak height) of nearby characteristic peaks3735/I3550Is 4-10.
The polyol preferably has a carbon number of C2-C12, more preferably C5-C8, and a hydroxyl number of at least 2, and further preferably hydroxyl groups are located on adjacent carbon atoms. Illustrative but non-exhaustive polyhydroxy compounds may be one or more of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, heptylene glycol, octylene glycol, nonylene glycol, decylene glycol, undecylene glycol, dodecylene glycol, glycerol, butanetriol, pentylene glycol, hexanetriol, heptanetriol, octylene glycol, butanetetraol, pentanetetraol, hexanetetrol, heptanetetraol, octanetetraol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclodecanediol, cycloundecanediol, cyclododecanediol, benzenediols (e.g. catechol, hydroquinone, resorcinol), methylbenzene diols, ethylbenzene diols, naphthalenediol, trioses (e.g. dihydroxyacetone), tetroses, pentoses (e.g. ribose, deoxyribose, ribulose), hexoses (e.g. glucose, fructose), heptoses, oligosaccharides (e.g. sucrose, maltose, lactose, cellobiose), or an isomer thereof.
The polyhydroxy compound is liquid containing polyhydroxy compound, and the mass fraction of the polyhydroxy compound in the liquid is 20-100%; the liquid containing the polyhydroxy compound can contain a solvent for dissolving the polyhydroxy compound, and the solvent is preferably C1-C10 alcohol, ketone, ether and ester. Preferably, the liquid containing the polyol is solvent free.
The molecular sieve N with skeleton hydroxyl vacancy is contacted with the polyhydroxy compound under the conditions of 5-100 ℃, preferably 40-80 ℃, 0.01-5MPa, preferably normal pressure, and the pressure is absolute pressure. The volume ratio of the liquid containing a polyol to the molecular sieve N is preferably (1-100):1, more preferably (5-70):1, and still more preferably (10-40): 1. The contact time can be 5min-24h, preferably 1h-4 h. The contacting may be dipping, mixing, stirring, fluid passing. The separation may be performed by a conventional separation method such as filtration and centrifugation, and the present invention is not particularly limited.
The zirconium source is an organic zirconium source and/or an inorganic zirconium source. Wherein the organic zirconium source is selected from the group consisting of zirconium n-propoxide, zirconium isopropoxide, zirconium n-butoxide, zirconocene dichloride, zirconium acetate, zirconium propionate, tetrabenzyl zirconium, tetrakis (ethylmethylamino) zirconium (IV), zirconium tetramethacrylate, zirconium hexafluoro-acetylacetonate, zirconocene hydrochloride, tetrabutyl zirconate, zirconium acetylacetonate, bis (n-butylcyclopentadienyl) zirconium dichloride, cyclopentadienyl zirconium trichloride, tetrakis (dimethylamino) zirconium, 1,1, 1-trifluoroacetylacetonate, pentamethylcyclopentadienyltrichloroquinolate (IV), tetraethoxyzirconium, tetrakis (2,2,6, 6-tetramethyl-3, 5-heptanedionate), bis (pentamethylcyclopentadienyl) zirconium dichloride, rac-ethylenebis (1-indenyl) zirconium dichloride, zirconium isooctanoate, biscyclopentadienyldimethyl zirconium, bis (cyclopentadienyl) zirconium dihydride, One or more of zirconium tert-butoxide, bis (methylcyclopentadienyl) zirconium dichloride, bis [ carbonic acid ] dihydroxydiammonium zirconate, bis (methylcyclopentadienyl) zirconium dichloride, bis (T-butylcyclopentadienyl) zirconium (IV) dichloride, tetrakis (ethylamino) zirconium, bis (isopropylcyclopentadienyl) zirconium dichloride, bis (1-butyl-3-methylcyclopentadienyl) zirconium dichloride; the inorganic zirconium source is selected from one or more of zirconium tetrachloride, zirconium sulfate, zirconium nitrate, zirconyl nitrate, zirconium carbonate, zirconium fluoride, ammonium fluorozirconate, potassium fluorozirconate, zirconium hydroxide and zirconium oxychloride.
The liquid P containing a zirconium source comprises a solvent which can dissolve the zirconium source, wherein the solvent is selected from C1-C10 alcohol, ketone, ether, ester, water and the like, and the preferred solvent is C1-C6 alcohol, ketone, ether and ester. In the liquid containing the zirconium source, the mass fraction of the zirconium source may be 5 to 30%, preferably 10 to 20%.
The contact of the molecular sieve O and the liquid P containing the zirconium source is carried out at 5-100 ℃, preferably 30-60 ℃, 0.01-5MPa, preferably normal pressure, absolute pressure and preferably 5-360 min. The contact may be performed by a solid-liquid contact method such as dipping or mixing. The liquid P contains zirconium element and molecular sieve O (SiO)2In terms of moles) may be (0.001-0.04):1, preferably (0.005-0.02):1, more preferably (0.008-0.015): 1.
The recovery of the product includes centrifugation, filtration, etc., and evaporation, preferably at atmospheric or reduced pressure, of the solvent. The recovered product further comprises a drying step at a temperature of 60-200 ℃, preferably 80-150 ℃, more preferably 100-.
In order to achieve the third object of the present invention, the present invention also provides an application of the zirconium-containing heteroatom molecular sieve, namely a method for catalyzing MPV reaction, which is characterized in that under MPV reaction conditions, the zirconium-containing heteroatom molecular sieve of the present invention is used as a catalyst to catalyze a carbonyl-containing compound to react with a secondary alcohol to generate a corresponding hydroxyl compound and ketone.
In the application, the carbonyl-containing compound can be a ketone with a carbon number of C3-C15, such as acetone, butanone, pentanone, cyclopentanone, hexanone, cyclohexanone, heptanone, octanone, cyclooctanone, cyclododecanone, levulinic acid. The carbon number of the secondary alcohol can be C3-C15, such as isopropanol, sec-butyl alcohol, sec-amyl alcohol, cyclopentanol, cyclohexanol, cyclohexanediol and cyclooctanol.
The zirconium-containing heteroatom molecular sieve has the advantages that the active center is enriched on the near surface, the molecular diffusion is facilitated, and the utilization rate of the active center is high.
The preparation method of the zirconium-containing heteroatom molecular sieve provided by the invention is simple in process and easy to implement.
The method for catalyzing MPV reaction provided by the invention has the advantages of high catalytic activity, good product yield and difficult inactivation of the active center.
Drawings
FIG. 1 shows the hydroxyl results of FT-IR measurement of beta molecular sieve N having skeletal hydroxyl vacancies in preparation example, 3550cm-1Nearby signal peaks can characterize the nest hydroxyl group, 3735cm-1The nearby signal peaks may characterize the terminal hydroxyl groups.
FIG. 2 is a representation of the molecular sieve sample in the micro-region of the transmission electron microscope spectrum.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
The infrared hydroxyl spectrogram of the molecular sieve sample adopts KBr tabletting and is measured by an FT-IR spectrometer, and the scanning range is 400-4000cm-1(ii) a Molecular sieve samplesThe XRF method is adopted for testing the chemical composition of the (A);
and (3) performing micro-area composition analysis on the molecular sieve crystal grains by adopting a TEM energy spectrum characterization method for the distribution of the zirconium element of the molecular sieve sample.
The raw materials used are analytically pure reagents, unless otherwise specified.
The reaction product is analyzed by gas chromatography, and the analysis result is quantified by an internal standard method. Wherein, the chromatographic analysis conditions are as follows: agilent-6890 type chromatograph, 30m × 0.25mm HP-5 capillary column, sample amount of 0.5 μ L, and sample inlet temperature of 280 deg.C. The column temperature was maintained at 100 ℃ for 2min, then ramped up to 280 ℃ at a rate of 15 ℃/min and maintained for 3 min. FID detector, detector temperature 300 ℃.
The catalytic performance of the molecular sieve of the invention is illustrated in the examples of the preparation of gamma-valerolactone by reduction of levulinic acid through MPV reaction catalyzed by Zr-beta molecular sieve and further esterification, but the use of the molecular sieve of the invention is not limited thereby.
The reaction process of MPV levulinic acid to gamma valerolactone is shown as follows, wherein the step (1) is catalyzed by Zr-beta molecular sieve, and the step (2) can occur under non-catalytic conditions (such as heating).
Figure BDA0002609027570000071
In each of the examples and comparative examples:
levulinic acid conversion (%) (moles of levulinic acid in feed-moles of levulinic acid in product)/moles of levulinic acid in feed × 100%
Yield of gamma-valerolactone (%) -. gamma-valerolactone in the product/levulinic acid in the starting material. times.100%
Preparation example 1
This preparation illustrates the preparation of beta molecular sieve N having framework hydroxyl vacancies.
50g (dry basis) of silicon-aluminum beta molecular sieve (silicon-aluminum ratio is 11) is added with water to prepare a molecular sieve solution with the solid content of 10 weight percent, and 13mol/LHNO is added in the stirring process3Heating to 100 deg.C, stirring at constant temperature for 20h, filtering, washing with water, and filteringAnd (3) neutralizing the solution, drying, and roasting at 550 ℃ for 2 hours to obtain the beta molecular sieve N1 with skeleton hydroxyl vacancies.
The beta molecular sieve and the beta molecular sieve N1 before and after the nitric acid dealumination treatment are subjected to XRF and FT-IR analysis tests. The FT-IR spectrum of beta molecular sieve N1 is shown in FIG. 1 and can be seen at 3550cm-1There is a characteristic peak near the molecular sieve, the absorption peak shows that part of framework aluminum of the molecular sieve is removed, I3735/I3550Is 4.3, and the silicon-aluminum ratio of the beta molecular sieve N1 after dealumination treatment is 1650.
Preparation example 2
This preparation illustrates the preparation of beta molecular sieve N having framework hydroxyl vacancies.
50g (dry basis) of silicon-aluminum beta molecular sieve (silicon-aluminum ratio is 24) is added with water to prepare a molecular sieve solution with the solid content of 10 weight percent, and 13mol/LHNO is added in the stirring process3Heating to 100 ℃, stirring at constant temperature for 20h, filtering, washing with water until the filtrate is neutral, drying, and roasting at 550 ℃ for 2h to obtain the beta molecular sieve N2 with skeleton hydroxyl vacancies.
The beta molecular sieve and the beta molecular sieve N2 before and after the nitric acid dealumination treatment are subjected to XRF and FT-IR analysis tests. The FT-IR spectrum of the beta molecular sieve N2 can be seen at 3550cm-1There is a characteristic peak near the molecular sieve, the absorption peak shows that part of framework aluminum of the molecular sieve is removed, I3735/I35509.5, and the silica-alumina ratio of beta molecular sieve N2 after dealumination treatment was 1836.
Example 1
Mixing the beta molecular sieve N1 obtained in the preparation example 1 and 1, 2-hexanediol according to the volume ratio of 1:10, treating for 2 hours at the temperature of 60 ℃ and under the normal pressure condition, and then filtering to obtain the molecular sieve O1.
Mixing zirconium oxychloride with ethanol to obtain liquid P1 containing a zirconium source, wherein the mass fraction of the zirconium oxychloride is 20%, and mixing the liquid P1 with a molecular sieve O1 at 50 ℃ and normal pressure for 30min, wherein the molar ratio of zirconium element in the liquid P1 to the molecular sieve O1 (calculated as SiO 2) is 0.01: 1. And (3) evaporating the solvent to dryness under reduced pressure to obtain a molecular sieve solid, and further drying at 120 ℃ for 12h and roasting at 550 ℃ for 6h to obtain a zirconium-containing heteroatom molecular sieve sample with the number of R1.
XRF and transmission electron microscopy spectroscopy characterization was performed on R1, and the results are shown in FIG. 2 and Table 1.
Evaluation reaction: mixing R1 with levulinic acid and sec-butyl alcohol, wherein the weight ratio of an R1 molecular sieve to the levulinic acid is 0.05:1, the molar ratio of the levulinic acid to the sec-butyl alcohol is 1:20, the reaction temperature is 80 ℃, the reaction time is 4 hours, and after the reaction is finished, separating a liquid phase product for chromatographic analysis. The catalyst was separated and the reaction was repeated 9 times under the same conditions and the 10 th reaction results were recorded. The evaluation results are shown in Table 2.
Example 2
Mixing the molecular sieve N1 obtained in the preparation example 1 and 1, 2-cyclohexanediol according to the volume ratio of 1:30, treating for 1h at 40 ℃ under normal pressure, and filtering to obtain the molecular sieve O2.
Zirconium tetrachloride and ethanol are mixed to obtain liquid P2 containing a zirconium source, wherein the mass fraction of the zirconium tetrachloride is 10%, and then the liquid P2 and a molecular sieve O2 are mixed and treated for 60min at the temperature of 30 ℃ and under the normal pressure, wherein the molar ratio of zirconium element in the liquid P2 to the molecular sieve O2 (calculated as SiO 2) is 0.008: 1. And (3) evaporating the solvent to dryness under reduced pressure to obtain a molecular sieve solid, and further drying at 110 ℃ for 12h and roasting at 500 ℃ for 12h to obtain a zirconium-containing heteroatom molecular sieve sample with the number of R2.
XRF and transmission electron microscopy energy spectrum characterization is carried out on R2, and the results are shown in Table 1.
Evaluation reaction: mixing R2 with levulinic acid and sec-butyl alcohol, wherein the weight ratio of an R2 molecular sieve to the levulinic acid is 0.05:1, the molar ratio of the levulinic acid to the sec-butyl alcohol is 1:20, the reaction temperature is 80 ℃, the reaction time is 4 hours, and after the reaction is finished, separating a liquid phase product for chromatographic analysis. The catalyst was separated and the reaction was repeated 9 times under the same conditions and the 10 th reaction results were recorded. The evaluation results are shown in Table 2.
Example 3
Mixing the molecular sieve N1 obtained in the preparation example 1 and 1, 2-octanediol according to a volume ratio of 1:20, treating at 80 ℃ for 3 hours under normal pressure, and then centrifuging to obtain the molecular sieve O3.
Mixing zirconium n-propoxide with n-propanol to obtain liquid P3 containing a zirconium source, wherein the mass fraction of the zirconium n-propoxide is 15%, and mixing the liquid P3 with a molecular sieve O3 at 60 ℃ and normal pressure for 120min, wherein the molar ratio of zirconium element in the liquid P3 to the molecular sieve O3 (calculated as SiO 2) is 0.013: 1. And (3) evaporating the solvent to obtain a molecular sieve solid, further drying at 150 ℃ for 6h, and roasting at 500 ℃ for 6h to obtain a heteroatom molecular sieve sample with zirconium-rich surface, wherein the number of the heteroatom molecular sieve sample is R3.
XRF and transmission electron microscopy energy spectrum characterization is carried out on R3, and the results are shown in Table 1.
Evaluation reaction: mixing R3 with levulinic acid and sec-butyl alcohol, wherein the weight ratio of the R3 molecular sieve to the levulinic acid is 0.05:1, the molar ratio of the levulinic acid to the sec-butyl alcohol is 1:20, the reaction temperature is 80 ℃, the reaction time is 4h, and after the reaction is finished, separating a liquid phase product for chromatographic analysis. The catalyst was separated and the reaction was repeated 9 times under the same conditions and the 10 th reaction results were recorded. The evaluation results are shown in Table 2.
Example 4
Mixing the molecular sieve N1 obtained in the preparation example 1 and 1, 2-hexanediol according to the volume ratio of 1:40, treating for 4 hours at the temperature of 50 ℃ and under the normal pressure condition, and then centrifuging to obtain the molecular sieve O4.
Mixing zirconium oxychloride with methanol to obtain liquid P4 containing a zirconium source, wherein the mass fraction of the zirconium oxychloride is 20%, and mixing the liquid P4 with a molecular sieve O4 at 40 ℃ and normal pressure for 90min, wherein the molar ratio of zirconium element in the liquid P4 to the molecular sieve O4 (calculated as SiO 2) is 0.01: 1. And (3) evaporating the solvent to dryness under reduced pressure to obtain a molecular sieve solid, further drying at 120 ℃ for 6h, and roasting at 550 ℃ for 6h to obtain a heteroatom molecular sieve sample with zirconium-rich surface, wherein the sample is numbered R4.
XRF and transmission electron microscopy energy spectrum characterization is carried out on R4, and the results are shown in Table 1.
Evaluation reaction: mixing R4 with levulinic acid and sec-butyl alcohol, wherein the weight ratio of the R4 molecular sieve to the levulinic acid is 0.05:1, the molar ratio of the levulinic acid to the sec-butyl alcohol is 1:20, the reaction temperature is 80 ℃, the reaction time is 4h, and after the reaction is finished, separating a liquid phase product for chromatographic analysis. The catalyst was separated and the reaction was repeated 9 times under the same conditions and the 10 th reaction results were recorded. The evaluation results are shown in Table 2.
Example 5
Mixing the molecular sieve N1 obtained in the preparation example 1 and 1, 2-cyclopentanediol according to the volume ratio of 1:10, treating for 3 hours at the temperature of 60 ℃ and under the normal pressure, and then centrifuging to obtain the molecular sieve O5.
Zirconium nitrate and butanone are mixed to obtain liquid P5 containing a zirconium source, wherein the mass fraction of the zirconium nitrate is 15%, and then the liquid P5 and a molecular sieve O5 are mixed and treated for 180min at the temperature of 30 ℃ and under the normal pressure, wherein the molar ratio of zirconium element in the liquid P5 to the molecular sieve O5 (calculated as SiO 2) is 0.015: 1. And (3) evaporating the solvent to dryness under reduced pressure to obtain a molecular sieve solid, further drying at 100 ℃ for 3h, and roasting at 550 ℃ for 6h to obtain a heteroatom molecular sieve sample with zirconium-rich surface, wherein the sample is numbered R5.
XRF and transmission electron microscopy energy spectrum characterization is carried out on R5, and the results are shown in Table 1.
Evaluation reaction: mixing R5 with levulinic acid and sec-butyl alcohol, wherein the weight ratio of the R5 molecular sieve to the levulinic acid is 0.05:1, the molar ratio of the levulinic acid to the sec-butyl alcohol is 1:20, the reaction temperature is 80 ℃, the reaction time is 4h, and after the reaction is finished, separating a liquid phase product for chromatographic analysis. The catalyst was separated and the reaction was repeated 9 times under the same conditions and the 10 th reaction results were recorded. The evaluation results are shown in Table 2.
Example 6
Mixing the molecular sieve N1 obtained in the preparation example 1 and 1, 2-butanediol according to a volume ratio of 1:50, treating the mixture for 5 hours at the temperature of 30 ℃ and under the normal pressure condition, and then filtering the mixture to obtain the molecular sieve O6.
Mixing zirconium oxychloride with ethanol to obtain liquid P6 containing a zirconium source, wherein the mass fraction of the zirconium oxychloride is 30%, and mixing the liquid P6 with a molecular sieve O6 at 80 ℃ and normal pressure for 30min, wherein the molar ratio of zirconium element in the liquid P6 to the molecular sieve O6 (calculated as SiO 2) is 0.01: 1. And (3) evaporating the solvent to dryness under reduced pressure to obtain a molecular sieve solid, further drying at 120 ℃ for 12h, and roasting at 550 ℃ for 6h to obtain a heteroatom molecular sieve sample with zirconium-rich surface, wherein the sample is numbered R6.
XRF and transmission electron microscopy energy spectrum characterization is carried out on R6, and the results are shown in Table 1.
Evaluation reaction: mixing R6 with levulinic acid and sec-butyl alcohol, wherein the weight ratio of the R6 molecular sieve to the levulinic acid is 0.05:1, the molar ratio of the levulinic acid to the sec-butyl alcohol is 1:20, the reaction temperature is 80 ℃, the reaction time is 4h, and after the reaction is finished, separating a liquid phase product for chromatographic analysis. The catalyst was separated and the reaction was repeated 9 times under the same conditions and the 10 th reaction results were recorded. The evaluation results are shown in Table 2.
Example 7
Mixing the molecular sieve N1 obtained in the preparation example 1 and 1, 2-propylene glycol according to the volume ratio of 1:60, treating for 8 hours at the temperature of 10 ℃ and under the normal pressure condition, and then filtering to obtain the molecular sieve O7.
Zirconium nitrate and ethyl acetate are mixed to obtain liquid P7 containing a zirconium source, wherein the mass fraction of the zirconium nitrate is 5%, and then the liquid P7 and a molecular sieve O7 are mixed and treated for 60min at the temperature of 20 ℃ and under the normal pressure, wherein the molar ratio of zirconium element in the liquid P7 to the molecular sieve O7 (calculated as SiO 2) is 0.005: 1. And (3) evaporating the solvent to dryness under reduced pressure to obtain a molecular sieve solid, further drying at 140 ℃ for 12h, and roasting at 550 ℃ for 6h to obtain a heteroatom molecular sieve sample with zirconium-rich surface, wherein the sample is numbered R7.
XRF and transmission electron microscopy energy spectrum characterization is carried out on R7, and the results are shown in Table 1.
Evaluation reaction: mixing R7 with levulinic acid and sec-butyl alcohol, wherein the weight ratio of the R7 molecular sieve to the levulinic acid is 0.05:1, the molar ratio of the levulinic acid to the sec-butyl alcohol is 1:20, the reaction temperature is 80 ℃, the reaction time is 4h, and after the reaction is finished, separating a liquid phase product for chromatographic analysis. The catalyst was separated and the reaction was repeated 9 times under the same conditions and the 10 th reaction results were recorded. The evaluation results are shown in Table 2.
Example 8
Mixing the molecular sieve N1 obtained in the preparation example 1 and 1, 4-butanediol according to a volume ratio of 1:80, treating for 6 hours at 20 ℃ and under normal pressure, and then filtering to obtain the molecular sieve O8.
Mixing zirconium n-propoxide with acetone to obtain a liquid P8 containing a zirconium source, wherein the mass fraction of the zirconium n-propoxide is 25%, and mixing the liquid P8 with a molecular sieve O8 at 70 ℃ and normal pressure for 120min, wherein the molar ratio of zirconium element in the liquid P8 to the molecular sieve O8 (calculated as SiO 2) is 0.02: 1. And (3) evaporating the solvent to dryness under reduced pressure to obtain a molecular sieve solid, and further drying at 100 ℃ for 18h and roasting at 600 ℃ for 6h to obtain a heteroatom molecular sieve sample with zirconium-rich surface, wherein the sample is numbered R8.
XRF and transmission electron microscopy energy spectrum characterization is carried out on R8, and the results are shown in Table 1.
Evaluation reaction: mixing R8 with levulinic acid and sec-butyl alcohol, wherein the weight ratio of the R8 molecular sieve to the levulinic acid is 0.05:1, the molar ratio of the levulinic acid to the sec-butyl alcohol is 1:20, the reaction temperature is 80 ℃, the reaction time is 4h, and after the reaction is finished, separating a liquid phase product for chromatographic analysis. The catalyst was separated and the reaction was repeated 9 times under the same conditions and the 10 th reaction results were recorded. The evaluation results are shown in Table 2.
Example 9
This example was used to prepare surface zirconium-rich beta molecular sieves and to evaluate the reaction.
Mixing the molecular sieve N1 obtained in the preparation example 1 with glycerol according to the volume ratio of 1:70, processing for 24 hours at the temperature of 100 ℃ and under the normal pressure, and then filtering to obtain the molecular sieve O9.
Mixing zirconium oxychloride with methanol to obtain liquid P9 containing a zirconium source, wherein the mass fraction of the zirconium oxychloride is 8%, and mixing the liquid P9 with a molecular sieve O9 at 80 ℃ and normal pressure for 120min, wherein the molar ratio of zirconium element in the liquid P9 to the molecular sieve O9 (calculated as SiO 2) is 0.015: 1. And (3) evaporating the solvent to dryness under reduced pressure to obtain a molecular sieve solid, and further drying at 110 ℃ for 5h and roasting at 550 ℃ for 6h to obtain a heteroatom molecular sieve sample with zirconium-rich surface, wherein the sample is numbered R9.
XRF and transmission electron microscopy energy spectrum characterization is carried out on R9, and the results are shown in Table 1.
Evaluation reaction: mixing R9 with levulinic acid and sec-butyl alcohol, wherein the weight ratio of the R9 molecular sieve to the levulinic acid is 0.05:1, the molar ratio of the levulinic acid to the sec-butyl alcohol is 1:20, the reaction temperature is 80 ℃, the reaction time is 4h, and after the reaction is finished, separating a liquid phase product for chromatographic analysis. The catalyst was separated and the reaction was repeated 9 times under the same conditions and the 10 th reaction results were recorded. The evaluation results are shown in Table 2.
Example 10
This example was used to prepare surface zirconium-rich beta molecular sieves and to evaluate the reaction.
Mixing the molecular sieve N1 obtained in the preparation example 1 with a mixture of naphthalenediol and ethanol according to a volume ratio of 1:50, wherein the weight fraction of the naphthalenediol in the mixture of the naphthalenediol and the ethanol is 50%, treating for 12h at 30 ℃ under normal pressure, and filtering to obtain the molecular sieve O10.
Zirconium tetrachloride and butanol are mixed to obtain liquid P10 containing a zirconium source, wherein the mass fraction of the zirconium tetrachloride is 25%, and then the liquid P10 and a molecular sieve O10 are mixed and treated for 240min at 100 ℃ and normal pressure, wherein the molar ratio of zirconium element in the liquid P10 to the molecular sieve O10 (calculated as SiO 2) is 0.04: 1. And (3) evaporating the solvent to dryness under reduced pressure to obtain a molecular sieve solid, further drying at 120 ℃ for 5h, and roasting at 550 ℃ for 12h to obtain a heteroatom molecular sieve sample with zirconium-rich surface, wherein the sample is numbered R10.
XRF and transmission electron microscopy energy spectrum characterization is carried out on R10, and the results are shown in Table 1.
Evaluation reaction: mixing R10 with levulinic acid and sec-butyl alcohol, wherein the weight ratio of the R10 molecular sieve to the levulinic acid is 0.05:1, the molar ratio of the levulinic acid to the sec-butyl alcohol is 1:20, the reaction temperature is 80 ℃, the reaction time is 4h, and after the reaction is finished, separating a liquid phase product for chromatographic analysis. The catalyst was separated and the reaction was repeated 9 times under the same conditions and the 10 th reaction results were recorded. The evaluation results are shown in Table 2.
Example 11
This example was used to prepare surface zirconium-rich beta molecular sieves and to evaluate the reaction.
In contrast to example 1, zirconium-containing heteroatom molecular sieve R11 was prepared from beta molecular sieve N2 obtained in preparation example 2, and characterization and evaluation reactions were carried out, and the results are shown in tables 1 and 2.
Comparative example 1
This comparative example is used to illustrate a hydrothermally synthesized Zr — beta molecular sieve and to evaluate the reaction.
Reference method for hydrothermal synthesis of Zr- β molecular sieves in fluorine-containing systems (RSC adv.,2014,4, 13481-.
10.42g tetraethyl silicate was weighed into a mixture with 10.31g tetraethylammonium hydroxide (40 wt% aqueous solution) and hydrolyzed with stirring. After 2h, 1.55g of an aqueous solution of zirconium oxychloride was added, wherein the molar ratio of zirconium to silicon was 0.01: 1. After stirring the resulting mixture for a further 8h, 1.215ml of HF solution (40% by weight) and 0.105g of pure silicon beta-molecular sieve were additionally seeded. And crystallizing the obtained mixture at 140 ℃ for 20 days, filtering and washing to obtain a solid product, drying the solid product at 120 ℃ for 12h, and roasting at 550 ℃ for 6h to obtain a Zr-beta molecular sieve comparison sample, wherein the number of the Zr-beta molecular sieve comparison sample is D1.
XRF and transmission electron microscopy spectroscopy characterization of D1 was performed, and the results are shown in Table 1.
Evaluation reaction: mixing D1 with levulinic acid and sec-butyl alcohol, wherein the weight ratio of a D1 molecular sieve to the levulinic acid is 0.05:1, the molar ratio of the levulinic acid to the sec-butyl alcohol is 1:20, the reaction temperature is 80 ℃, the reaction time is 4 hours, and after the reaction is finished, separating a liquid phase product for chromatographic analysis. The catalyst was separated and the reaction was repeated 9 times under the same conditions and the 10 th reaction results were recorded. The evaluation results are shown in Table 2.
Comparative example 2
This comparative example is used to illustrate the preparation of Zr-beta molecular sieves via post-synthesis zirconium insertion and to evaluate the reaction.
Zirconium oxychloride and ethanol are mixed to obtain liquid P11 containing a zirconium source, wherein the mass fraction of the zirconium oxychloride is 20%, and then the liquid P11 and the molecular sieve N of the preparation example are mixed and treated for 30min at 50 ℃ and normal pressure, wherein the molar ratio of zirconium element in the liquid P11 to the molecular sieve O1 (calculated as SiO 2) is 0.01: 1. And then evaporating the solvent to dryness under reduced pressure to obtain a molecular sieve solid, further drying the obtained molecular sieve solid at 120 ℃ for 12h, and roasting at 550 ℃ for 6h to obtain a Zr-beta molecular sieve comparison sample, wherein the sample is numbered D2.
XRF and transmission electron microscopy spectroscopy characterization of D2 was performed, and the results are shown in Table 1.
Evaluation reaction: mixing D2 with levulinic acid and sec-butyl alcohol, wherein the weight ratio of a D2 molecular sieve to the levulinic acid is 0.05:1, the molar ratio of the levulinic acid to the sec-butyl alcohol is 1:20, the reaction temperature is 80 ℃, the reaction time is 4 hours, and after the reaction is finished, separating a liquid phase product for chromatographic analysis. The catalyst was separated and the reaction was repeated 9 times under the same conditions and the 10 th reaction results were recorded. The evaluation results are shown in Table 2.
TABLE 1
Sample (I) Bulk Zr/Si (mol) (surface Zr/Si)/(Central Zr/Si) (mol)
Example 1 R1 0.01:1 29:1
Example 2 R2 0.008:1 24:1
Example 3 R3 0.013:1 42:1
Example 4 R4 0.01:1 34:1
Example 5 R5 0.015:1 48:1
Example 6 R6 0.01:1 17:1
Example 7 R7 0.005:1 10:1
Example 8 R8 0.02:1 65:1
Example 9 R9 0.015:1 57:1
Example 10 R10 0.04:1 86:1
Example 11 R11 0.01:1 22:1
Comparative example 1 D1 0.01:1 0.8:1
Comparative example 2 D2 0.01:1 1.2:1
As can be seen from table 1, the Zr- β molecular sieve provided by the present invention has a molar ratio of zirconium to silicon on the surface higher than that of zirconium to silicon in the central portion, and a molar ratio of zirconium to silicon in the surface to that of zirconium to silicon in the central portion is between 10 and 86, which is significantly higher than 0.8 and 1.2 of prior art D1 and D2, and has a significant property of surface zirconium enrichment.
TABLE 2
Figure BDA0002609027570000151
As can be seen from Table 2, when the Zr-beta molecular sieve provided by the invention is used for catalyzing levulinic acid to prepare gamma-valerolactone through MPV reaction, the Zr-beta molecular sieve has higher raw material conversion rate and product yield, and compared with a comparative example, the Zr-beta molecular sieve still has high raw material conversion rate and product yield after being used for 10 times, and has longer service life.
The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.

Claims (17)

1. A molecular sieve containing zirconium heteroatom, the molar ratio of zirconium to silicon at the surface part of the molecular sieve is higher than that at the central part, and the molar ratio of zirconium to silicon in the molecular sieve phase is (0.001-0.04): 1; the molar ratio of zirconium to silicon at the surface part of the molecular sieve and the molar ratio of zirconium to silicon at the central part of the molecular sieve are both characterized and measured by a TEM energy spectrum, and a rectangular selected area at the surface part of the molecular sieve and a rectangular selected area at the central part of the molecular sieve of a TEM morphology picture of a molecular sieve crystal grain are respectively selected as target spots for composition analysis; wherein the content of the first and second substances,
the rectangular selection area on the surface of the molecular sieve is characterized in that a tangent is made at the boundary of the molecular sieve crystal grain, an area which is perpendicular to the tangent and has a distance of less than 10nm is selected, the rectangular selection area is located in the area, and the overlapping area of the rectangular selection area and the molecular sieve crystal grain is 50-3000 nm2；
The central part of the molecular sieve is a rectangular selected area, the grain boundary of the molecular sieve is used as a boundary to make a maximum inscribed circle, 50% of the radius of the inscribed circle is used as a concentric circle, the rectangular selected area falls in the concentric circle, and the area of the rectangular selected area is 50-3000 nm2。
2. The molecular sieve of claim 1, wherein the ratio of the molar ratio of zirconium to silicon at the surface portion of the molecular sieve to the molar ratio of zirconium to silicon at the central portion of the molecular sieve is (1.5-200): 1.
3. the molecular sieve of claim 1, wherein the molecular sieve has a BEA structure.
4. A method for preparing a zirconium-containing heteroatom molecular sieve is characterized by comprising the steps of contacting a molecular sieve N with framework hydroxyl vacancies with a polyhydroxy compound, treating and separating to obtain a molecular sieve O, contacting the molecular sieve O with a liquid P containing a zirconium source, and recovering the product.
5. The process according to claim 4, wherein said skeleton hydroxyl vacancies have an IR hydroxyl spectrum at a wavenumber of 3550cm-1And a characteristic peak is obvious nearby.
6. The method of claim 4, wherein said molecular sieve N having framework hydroxyl vacancies is a silicoaluminophosphate molecular sieve with the framework hydroxyl vacancies removedThe infrared hydroxyl spectrogram of the molecular sieve after partial framework atoms is 3735cm-1The intensity and wave number of nearby characteristic peak are 3550cm-1Ratio I of intensities of nearby characteristic peaks3735/I3550Is 4 to 10.
7. The method according to claim 4, wherein the polyol has 2 to 12 carbon atoms and at least 2 hydroxyl groups.
8. The preparation method of claim 4, wherein the polyhydroxy compound is in contact treatment with the molecular sieve N with skeleton hydroxyl vacancy in the form of polyhydroxy compound-containing liquid, and the mass fraction of the polyhydroxy compound in the liquid is 20-100%; the liquid containing polyhydroxy compound contains solvent for dissolving polyhydroxy compound.
9. The process according to claim 8, wherein the solvent for dissolving the polyol is alcohol, ketone, ether or ester.
10. The preparation method of claim 4, wherein the contact treatment of the molecular sieve N with the skeleton hydroxyl vacancies and the polyhydroxy compound is carried out at 5-100 ℃ and 0.01-5MPa, and the pressure is absolute pressure.
11. The method according to claim 4, wherein the zirconium source is an organic zirconium source and/or an inorganic zirconium source.
12. The process according to claim 11, wherein the organic zirconium source is selected from the group consisting of zirconium n-propoxide, zirconium isopropoxide, zirconium n-butoxide, zirconocene dichloride, zirconium acetate, zirconium propionate, tetrabenzyl zirconium, tetrakis (ethylmethylamino) zirconium (IV), zirconium tetra-methylacrylate, zirconium hexafluoro-acetylacetonate, zirconocene hydrochloride, tetrabutyl zirconate, zirconium acetylacetonate, bis (n-butylcyclopentadienyl) zirconium dichloride, cyclopentadienyl zirconium trichloride, tetrakis (dimethylamino) zirconium, 1,1, 1-trifluoroacetylacetonate, pentamethylcyclopentadienyl zirconium (IV), tetraethoxyzirconium, tetrakis (2,2,6, 6-tetramethyl-3, 5-heptanedionate) zirconium, bis (pentamethylcyclopentadienyl) zirconium dichloride, rac-ethylenebis (1-indenyl) zirconium dichloride, zirconium isooctanoate, biscyclopentadienyldimethylzirconium, One or more of bis (cyclopentadienyl) zirconium dichloride, zirconium tert-butoxide, bis (methylcyclopentadienyl) zirconium dichloride, diammonium bis [ carbonate ] dihydroxyzirconate, bis (methylcyclopentadienyl) zirconium dichloride, bis (T-butylcyclopentadienyl) zirconium (IV) dichloride, tetrakis (ethylamino) zirconium, bis (isopropylcyclopentadienyl) zirconium dichloride, bis (1-butyl-3-methylcyclopentadienyl) zirconium dichloride; the inorganic zirconium source is selected from one or more of zirconium tetrachloride, zirconium sulfate, zirconium nitrate, zirconyl nitrate, zirconium carbonate, zirconium fluoride, ammonium fluorozirconate, potassium fluorozirconate, zirconium hydroxide and zirconium oxychloride.
13. The method according to claim 4, wherein the liquid P containing a zirconium source comprises a solvent which can dissolve the zirconium source and is selected from the group consisting of alcohols, ketones, ethers, esters and water having C1-C10.
14. The method according to claim 4, wherein the contacting of the molecular sieve O with the liquid P containing the zirconium source is carried out at 5 to 100 ℃ and 0.01 to 5MPa, and the pressure is absolute pressure.
15. The process according to claim 4, wherein the recovery of the product comprises the step of evaporating the solvent under normal pressure or reduced pressure.
16. The method according to claim 15, wherein the recovered product further comprises a drying step at a temperature of 60 to 200 ℃ under vacuum or atmospheric pressure and a calcination step at a temperature of 300 to 800 ℃ under oxygen-deficient or oxygen-enriched conditions.
17. A method for catalyzing MPV reaction, characterized in that, under MPV reaction conditions, a molecular sieve containing zirconium heteroatom as claimed in any one of claims 1 to 3 is used as a catalyst to catalyze the reaction of ketone and secondary alcohol to produce corresponding alcohol and ketone.
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