CN114057209B - 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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CN114057209B
CN114057209B CN202010748033.XA CN202010748033A CN114057209B CN 114057209 B CN114057209 B CN 114057209B CN 202010748033 A CN202010748033 A CN 202010748033A CN 114057209 B CN114057209 B CN 114057209B
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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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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 at the central part, and the molar ratio of zirconium to silicon in the molecular sieve body phase is (0.001-0.04): 1, a step of; the preparation method comprises the steps of contacting a molecular sieve N with skeleton hydroxyl vacancies with a polyhydroxy compound, 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, has high catalytic activity and good product yield, and the active center is not easy to be deactivated.

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 thereof and application thereof in the field of catalytic reduction reaction.
Background
The Zr-beta molecular sieve is a hetero-atom molecular sieve with four coordination Zr atoms in the molecular sieve framework and BEA topological structure. The zirconium atoms of the framework are Lewis acid, and meanwhile, the beta molecular sieve has a three-dimensional twelve-membered ring pore canal structure, so that the beta molecular sieve can be suitable for the 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 fructose isomerization), aldol condensation reaction, diene addition reaction (Diels-Alder reaction), MPV (Meerwein-Ponndorf-Verley) reaction and the like, and has important roles in preparing high-end fine chemicals.
The Zr-beta molecular sieve is prepared mainly through hydrothermal synthesis or through post-treatment synthesis of silicon-aluminum beta molecular sieve. The hydrothermal synthesis method needs to introduce fluoride ions or seed crystals, and the molecular sieve product is obtained through long-time crystallization treatment. The introduction of fluoride ions makes wastewater treatment difficult. In addition, the Zr-beta molecular sieve synthesized by adopting a fluoride ion system or adding seed crystals is generally large in grain size, reaching about a micron level (Catal. Sci. Technology., 2016,6,3018-3026).
Yongzhong Zhu et al (CHEM. COMMUN.,2003, p 2734-2735) used TEOS (tetraethyl silicate) as the silicon source, TEAOH (tetraethylammonium hydroxide) as the alkali source and templating agent, zrOCl 2 ·8H 2 O is a zirconium source, HF (hydrofluoric acid) aqueous solution is a mineralizer, meanwhile, dealuminated beta molecular sieve is added as seed crystal, and the Zr-beta molecular sieve is obtained after hydrothermal crystallization treatment for 5-30 days at 140-170 ℃. 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 adopting the hydrothermal synthesis method has the defects of short service life and easy inactivation in the MPV reaction (Catal. Sci. Technology., 2016,6,3018-3026).
The Zr-beta molecular sieve is synthesized by adopting the post-treatment of the silicon aluminum beta molecular sieve without crystallization, fluorine-containing compounds and organic template agents, and the preparation process is simple and efficient, so that the preparation method is paid attention to.
Gang Li et al (ACS Sustainable chem. Eng.2018,6, 4316-4320) employed 7.2MHNO 3 (55 mL per gram molecular sieve) after aluminum removal by treatment of the silica alumina beta molecular sieve at 80℃for 4 hours, zr (NO) was dissolved again 3 ) 4 ·5H 2 O ethanol solution is treated to insert zirconium atoms, and solid powder is dried, roasted and then treated by sodium hydroxide solution to obtain Zr-beta molecular sieve; when the Zr-beta molecular sieve is used in the MPV reaction of the furfural derivative, the conversion rate of raw materials and the yield of target products are lower.
Bo Tang et al (Green chem.,2015,17,1744) treated silica alumina beta molecular sieves with oxalic acid solution for partial removalThe aluminum is then reamed by alkali treatment, then dealuminated for 20 hours by a nitric acid solution of 13mol/L to obtain a mesoporous-rich all-silicon beta molecular sieve, and finally the mesoporous-rich all-silicon beta molecular sieve is mixed with zirconium source zirconocene dichloride (Cp 2 ZrCl) 2 ) 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 catalyst preparation process is too complex.
The Zr-beta molecular sieve synthesized directly through hydrothermal has more uniform distribution of zirconium species, but the problems of pore blocking, inactivation and the like are easily caused by large diffusion resistance of compound molecules in the molecular sieve due to large crystal grains of the molecular sieve. The Zr-beta molecular sieve is prepared by adopting post synthesis, and the prepared Zr-beta molecular sieve has the problems of low activity, short service life and the like due to the aluminum species distribution of the parent silicon aluminum beta molecular sieve. Although the mesoporous Zr-beta molecular sieve prepared by post-treatment can alleviate the problem, the preparation process is complex and difficult to apply on a large scale. In view of the above, development of a novel Zr- β molecular sieve is urgently needed to solve the problems of low activity and short lifetime of molecular sieves caused by large diffusion resistance of molecules in the existing Zr- β 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 in the application process of the existing zirconium-containing molecular sieve. It is a further object of the present invention to provide a use of the molecular sieve.
In order to achieve one of the purposes of the invention, the molecular sieve containing zirconium heteroatoms provided by the invention has a molar ratio of zirconium to silicon at the surface part of the molecular sieve which is higher than that at the central part, and the molar ratio of zirconium to silicon in the molecular sieve body phase is (0.001-0.04): 1, a step of; 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 respectively determined by TEM energy spectrum characterization, and rectangular selective areas at the surface part of the molecular sieve and rectangular selective areas at the central part of the molecular sieve of TEM morphology pictures of the molecular sieve crystal grains are respectively selected as target points for composition analysis; wherein,,
the said processThe rectangular selective area of the molecular sieve surface is that a tangent line is made on the boundary of the molecular sieve crystal grain, a region which is perpendicular to the tangent line and has a distance of less than 10nm is selected, the rectangular selective area is located in the region, and the overlapping area of the rectangular selective area and the molecular sieve crystal grain is 50-3000 nm 2 ；
The rectangular selective area at the center of the molecular sieve takes the grain boundary of the molecular sieve as the smallest inscribed circle and takes 50 percent of the radius of the inscribed circle as the concentric circle, the rectangular selective area is positioned in the concentric circle, and the area of the rectangular selective area is 50-3000 nm 2 。
When the molecular sieve is measured by using TEM energy spectrum, rectangular selected 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 body phase is (0.001-0.04): 1. preferably (0.005-0.02): 1, more preferably (0.008-0.015): 1.
In the invention, zirconium element in the molecular sieve is mainly enriched on the surface of the molecular sieve. The molar ratio of zirconium to silicon at the surface of the molecular sieve to the molar ratio of zirconium to silicon at the center of the molecular sieve can be (1.5-200) as characterized by TEM energy spectrum: 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, and preferably, but not limited to, BEA structures, MWW, CON, EWT, MSE, ITN, IFR, DON, CFI, UTL, OKO and the like structures are also suitable for the type of molecular sieve of the present invention. The molecular sieve is not limited to the types and the contents of elements, and besides zirconium element, the molecular sieve can also contain at least one element of aluminum, boron, titanium, tin, vanadium, cobalt, chromium, hafnium, tantalum, tungsten and lead, wherein the molar ratio of the element to silicon is (0-0.04): 1, preferably zirconium alone is the heteroatom element.
In order to achieve the second object of the present invention, the present invention also provides a method for preparing the molecular sieve containing zirconium hetero atoms, which is characterized in that the method comprises the steps of contacting the molecular sieve N having skeleton hydroxyl vacancies with a polyhydroxy compound and separating to obtain a molecular sieve O, and then contacting the 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 adopting direct synthesis such as hydrothermal synthesis method, or can be obtained by adopting post-treatment such as removing part of skeleton atoms, for example, acid treatment, alkali treatment, high-temperature hydrothermal treatment or microwave treatment and other methods are adopted to remove part of skeleton atoms. Preferably by a post-treatment process. Preferably, the parent molecular sieve used in the post-treatment is a silica-alumina molecular sieve.
The skeleton hydroxyl vacancy refers to the infrared hydroxyl spectrum of the material with the wave number of 3550cm -1 There are distinct characteristic peaks in the vicinity. In the infrared hydroxyl spectrogram of the molecular sieve, 3550cm -1 The nearby signal peak can characterize the nest hydroxyl group, 3735cm -1 The nearby signal peaks may characterize the terminal hydroxyl groups. The molecular sieve N is a silicon-aluminum molecular sieve, and the infrared hydroxyl spectrogram of the molecular sieve N is 3735cm after part of framework atoms are removed -1 Characteristic peak intensity (in terms of peak height) and wavenumber at 3550cm -1 Ratio I of nearby characteristic peak intensities (in terms of peak heights) 3735 /I 3550 4-10.
The polyhydroxy compound preferably has a carbon number of C2-C12, more preferably C5-C8, and a hydroxyl number of at least 2, and further preferably has hydroxyl groups on adjacent carbon atoms. Illustrative but non-exhaustive polyols 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, pentylmethanol, hexanetriol, octatetrol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctadecylene glycol, cycloundecylene glycol, cyclododecylene glycol, benzenediol (e.g., catechol, hydroquinone, resorcinol), methylbenzenediol, ethylbenzenediol, naphthalenediol, tricarbosaccharides (e.g., dihydroxyacetone), tetracarbonates, pentasaccharides (e.g., ribose, deoxyribose, ribulose), hexasaccharides (e.g., glucose, fructose), heptose, oligosaccharides (e.g., sucrose, maltose, lactose, cellobiose), or isomers thereof.
The polyhydroxy compound is a liquid containing polyhydroxy compound, and the mass fraction of the polyhydroxy compound in the liquid is 20-100%; the polyol-containing liquid may contain a solvent for dissolving the polyol, and the solvent is preferably a C1-C10 alcohol, ketone, ether or ester. Preferably, the polyol-containing liquid is free of solvent.
The contact of the molecular sieve N with skeleton hydroxyl vacancies and the polyhydroxy compound is carried out 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 polyol-containing liquid to the molecular sieve N is preferably (1-100): 1, more preferably (5-70): 1, still more preferably (10-40): 1. The contact time may be 5min to 24h, preferably 1h to 4h. The contact can be dipping, mixing and stirring, and fluid passing. The separation may be performed in a manner conventionally used for separation, 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 zirconium n-propoxide, zirconium isopropoxide, zirconium n-butoxide, zirconocene dichloride, zirconium acetate, zirconium propionate, zirconium tetrabenzyl, zirconium tetra (ethylmethylamino) dichloride (IV), zirconium tetramethyl acrylate, zirconium hexafluoro-acetylacetonate, zirconium chlorodicyclopentadiene, tetrabutyl zirconate, zirconium acetylacetonate, zirconium bis (n-butylcyclopentadienyl) dichloride, zirconium cyclopentadienyl trichloride, zirconium tetra (dimethylamino) 1, 1-trifluoroacetylacetonate, zirconium pentamethylcyclopentadienyl trichloride (IV), zirconium tetraethoxide, zirconium tetra (2, 6-tetramethyl-3, 5-heptanedioate), zirconium bis (pentamethylcyclopentadienyl) dichloride, rac-ethylene bis (1-indenyl) zirconium dichloride, zirconium isooctanoate, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) zirconium hydride, zirconium tert-butoxide, bis (methylcyclopentadienyl) dichloride, bis [ carbonate ] diammonium zirconium dichloride, bis (methyl) cyclopentadienyl) dicyclopentadiene dichloride, bis (T-cyclopentadienyl) dicyclopentadiene, bis (cyclopentadienyl) bis (3-zirconium) di (methyl) cyclopentadienyl) dichloride, bis (cyclopentadienyl) bis (3-zirconium) di (isopropyl) dichloride, bis (cyclopentadienyl) zirconium (1-bis (isopropyl) dichloride; the inorganic zirconium source is one or more selected from zirconium tetrachloride, zirconium sulfate, zirconium nitrate, zirconyl nitrate, zirconium carbonate, zirconium fluoride, ammonium fluorozirconate, potassium fluorozirconate, zirconium hydroxide and zirconium oxychloride.
The zirconium source-containing liquid P contains a zirconium source-soluble solvent selected from alcohols, ketones, ethers, esters, or water having C1-C10, and the like, with the preferred solvents being C1-C6 alcohols, ketones, ethers, esters. The mass fraction of the zirconium source in the liquid containing the zirconium source may be 5-30%, preferably 10-20%.
The contact of the molecular sieve O with the liquid P containing the zirconium source is carried out at 5-100 ℃, preferably 30-60 ℃,0.01-5MPa, preferably at normal pressure, the pressure is absolute pressure, and the contact time is preferably 5-360min. The contacting may be performed by solid-liquid contact such as dipping, mixing and stirring. The zirconium element in the liquid P and the molecular sieve O (SiO 2 The molar ratio 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 is preferably carried out at normal pressure or reduced pressure to evaporate the solvent. The recovered product may further comprise a drying step at a temperature of 60 to 200 c, preferably 80 to 150 c, more preferably 100 to 130 c, under vacuum or atmospheric conditions, and a calcination step at an oxygen-depleted or oxygen-enriched, 300 to 800 c, preferably 400 to 700 c, more preferably 500 to 600 c.
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, that is, a method for catalyzing MPV reaction, which is characterized in that under the MPV reaction condition, 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 said application, said carbonyl-containing compound may be a C3-C15 ketone, such as acetone, butanone, pentanone, cyclopentanone, hexanone, cyclohexanone, heptanone, octanone, cyclooctanone, cyclododecanone, levulinic acid. The secondary alcohol may have a carbon number of C3-C15, such as isopropanol, sec-butanol, sec-amyl alcohol, cyclopentanol, cyclohexanol, cyclohexanediol, cyclooctanol.
The zirconium-containing heteroatom molecular sieve disclosed by the invention has the advantages that the active centers are enriched on the near surface, the molecular diffusion is facilitated, and the utilization rate of the active centers is high.
The preparation method of the zirconium-containing heteroatom molecular sieve provided by the invention is simple in flow and easy to implement.
The method for catalyzing the MPV reaction has the advantages of high catalytic activity, good product yield and difficult inactivation of the active center.
Drawings
FIG. 1 shows the results of FT-IR of beta molecular sieves N having a backbone hydroxyl vacancy in preparation, 3550cm -1 The nearby signal peak can characterize the nest hydroxyl group, 3735cm -1 The nearby signal peaks may characterize the terminal hydroxyl groups.
FIG. 2 is a representation of molecular sieve sample transmission electron microscopy spectral microzones.
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 is pressed by KBr and measured by FT-IR spectrometer, and the scanning range is 400-4000cm -1 The method comprises the steps of carrying out a first treatment on the surface of the The chemical composition of the molecular sieve sample is tested by an XRF method;
the zirconium element distribution of the molecular sieve sample adopts a TEM energy spectrum characterization method to carry out micro-region composition analysis on the molecular sieve crystal grains.
All raw materials 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, chromatographic analysis conditions are: agilent-6890 chromatograph, 30m×0.25mm HP-5 capillary column, sample injection amount 0.5 μL, sample injection port temperature 280 ℃. The column temperature was maintained at 100deg.C for 2min, then raised to 280℃at a rate of 15deg.C/min, and maintained for 3min. FID detector, detector temperature 300 ℃.
In the examples, the molecular sieve catalytic performance of the present invention is illustrated by the reduction of Zr-beta molecular sieve catalyzed levulinic acid via MPV reaction and further esterification to produce gamma valerolactone, but the use of the molecular sieve of the present invention is not limited thereby.
The reaction of levulinic acid MPV to gamma valerolactone is schematically shown below, wherein step (1) is catalyzed by Zr-beta molecular sieves and step (2) may occur under non-catalytic conditions (e.g. heating).
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 x 100%
Gamma valerolactone yield (%) = moles of gamma valerolactone in product/moles of levulinic acid in starting material x 100%
Preparation example 1
This preparation illustrates the preparation of beta molecular sieves N having a backbone hydroxyl vacancy.
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 stirring 3 Heating to 100 ℃, stirring for 20 hours at constant temperature, filtering, washing with water until the filtrate is neutral, drying, and roasting at 550 ℃ for 2 hours to obtain the beta molecular sieve N1 with skeleton hydroxyl vacancies.
And (3) carrying out XRF and FT-IR analysis tests on the beta molecular sieve and the beta molecular sieve N1 before and after the nitric acid dealumination treatment. FT-IR spectrum of beta molecular sieve N1 is shown in FIG. 1, and can be seen at 3550cm -1 The vicinity has characteristic peaks which indicate that part of framework aluminum of the molecular sieve is removed, I 3735 /I 3550 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 sieves N having a backbone hydroxyl vacancy.
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 stirring 3 Heating to 100deg.C and keeping constant temperatureStirring 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.
And (3) carrying out XRF and FT-IR analysis tests on the beta molecular sieve and the beta molecular sieve N2 before and after the nitric acid dealumination treatment. The FT-IR spectrum of beta molecular sieve N2 is found at 3550cm -1 The vicinity has characteristic peaks which indicate that part of framework aluminum of the molecular sieve is removed, I 3735 /I 3550 9.5, and the silicon-aluminum ratio of the beta molecular sieve N2 after dealumination treatment is 1836.
Example 1
The beta molecular sieve N1 obtained in preparation example 1 and 1, 2-hexanediol are mixed according to the volume ratio of 1:10, treated for 2 hours at 60 ℃ and normal pressure, and then filtered to obtain the molecular sieve O1.
Zirconium oxychloride is mixed with ethanol to obtain a liquid P1 containing a zirconium source, wherein the mass fraction of the zirconium oxychloride is 20%, and then the liquid P1 and the molecular sieve O1 are mixed and treated for 30 minutes at 50 ℃ under normal pressure, wherein the molar ratio of zirconium element to the molecular sieve O1 (calculated by SiO 2) in the liquid P1 is 0.01:1. The solvent is evaporated to dryness under reduced pressure to obtain molecular sieve solid, and the molecular sieve solid is further dried at 120 ℃ for 12 hours and baked at 550 ℃ for 6 hours to obtain a zirconium-containing heteroatom molecular sieve sample, and the molecular sieve sample is numbered R1.
XRF and transmission electron microscopy spectra characterization was performed on R1, and the results are shown in fig. 2 and table 1.
Evaluation of the reaction: mixing R1 with levulinic acid and sec-butyl alcohol, wherein the weight ratio of the R1 molecular sieve to the levulinic acid is 0.05:1, the mol 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 separating a liquid phase product after the reaction is finished for chromatographic analysis. The catalyst was separated, the reaction was repeated 9 times under the same conditions, and the 10 th reaction result was recorded. The evaluation results are shown in Table 2.
Example 2
The molecular sieve N1 obtained in preparation example 1 and 1, 2-cyclohexanediol are mixed according to a volume ratio of 1:30, treated for 1h at 40 ℃ under normal pressure, and then filtered to obtain the molecular sieve O2.
Zirconium tetrachloride and ethanol are mixed to obtain a liquid P2 containing a zirconium source, wherein the mass fraction of the zirconium tetrachloride is 10%, and then the liquid P2 and the molecular sieve O2 are mixed and treated for 60 minutes at the temperature of 30 ℃ and under the normal pressure, wherein the mol ratio of zirconium element to the molecular sieve O2 (calculated by SiO 2) in the liquid P2 is 0.008:1. The solvent is evaporated to dryness under reduced pressure to obtain molecular sieve solid, and the molecular sieve solid is further dried at 110 ℃ for 12 hours and baked at 500 ℃ for 12 hours to obtain a zirconium-containing heteroatom molecular sieve sample, with the number of R2.
XRF and transmission electron spectroscopy characterization was performed on R2, and the results are shown in table 1.
Evaluation of the reaction: mixing R2 with levulinic acid and sec-butyl alcohol, wherein the weight ratio of the R2 molecular sieve to the levulinic acid is 0.05:1, the mol 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 separating a liquid phase product after the reaction is finished for chromatographic analysis. The catalyst was separated, the reaction was repeated 9 times under the same conditions, and the 10 th reaction result was recorded. The evaluation results are shown in Table 2.
Example 3
The molecular sieve N1 obtained in preparation example 1 and 1, 2-octanediol are mixed according to the volume ratio of 1:20, treated for 3 hours at 80 ℃ and normal pressure, and then centrifuged to obtain the molecular sieve O3.
Zirconium n-propoxide and n-propanol are mixed to obtain a liquid P3 containing a zirconium source, wherein the mass fraction of the zirconium n-propoxide is 15%, and then the liquid P3 and the molecular sieve O3 are mixed and treated for 120min under the conditions of 60 ℃ and normal pressure, wherein the molar ratio of zirconium element to the molecular sieve O3 (calculated as SiO 2) in the liquid P3 is 0.013:1. Evaporating the solvent to obtain molecular sieve solid, further drying at 150 ℃ for 6 hours, and roasting at 500 ℃ for 6 hours to obtain a heteroatom molecular sieve sample with zirconium-enriched surface, number R3.
XRF and transmission electron microscopy spectra characterization was performed on R3 and the results are shown in table 1.
Evaluation of the reaction: r3 is mixed 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 mol 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, the liquid phase product is separated for chromatographic analysis. The catalyst was separated, the reaction was repeated 9 times under the same conditions, and the 10 th reaction result was recorded. The evaluation results are shown in Table 2.
Example 4
The molecular sieve N1 obtained in preparation example 1 and 1, 2-hexanediol are mixed according to a volume ratio of 1:40, treated for 4 hours at 50 ℃ and normal pressure, and then centrifuged to obtain the molecular sieve O4.
Zirconium oxychloride is mixed with methanol to obtain a liquid P4 containing a zirconium source, wherein the mass fraction of the zirconium oxychloride is 20%, and then the liquid P4 and the molecular sieve O4 are mixed and treated for 90 minutes at 40 ℃ under normal pressure, wherein the molar ratio of zirconium element to the molecular sieve O4 (calculated as SiO 2) in the liquid P4 is 0.01:1. And (3) evaporating the solvent under reduced pressure to obtain molecular sieve solid, further drying at 120 ℃ for 6 hours, and roasting at 550 ℃ for 6 hours to obtain a heteroatom molecular sieve sample with zirconium-enriched surface, and the number is R4.
XRF and transmission electron spectroscopy characterization was performed on R4 and the results are shown in table 1.
Evaluation of the reaction: r4 is mixed 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 mol 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, the liquid phase product is separated for chromatographic analysis. The catalyst was separated, the reaction was repeated 9 times under the same conditions, and the 10 th reaction result was recorded. The evaluation results are shown in Table 2.
Example 5
The molecular sieve N1 obtained in preparation example 1 and 1, 2-cyclopentanediol are mixed according to a volume ratio of 1:10, treated for 3 hours at 60 ℃ and normal pressure, and centrifuged to obtain a 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 the molecular sieve O5 are mixed and treated for 180 minutes under the conditions of 30 ℃ and normal pressure, wherein the mol ratio of zirconium element to the molecular sieve O5 (calculated as SiO 2) in the liquid P5 is 0.015:1. And (3) evaporating the solvent under reduced pressure to obtain molecular sieve solid, further drying at 100 ℃ for 3 hours, and roasting at 550 ℃ for 6 hours to obtain a heteroatom molecular sieve sample with zirconium-enriched surface, and the number is R5.
XRF and transmission electron microscopy spectra characterization was performed on R5 and the results are shown in table 1.
Evaluation of the reaction: r5 is mixed 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 mol 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, the liquid phase product is separated for chromatographic analysis. The catalyst was separated, the reaction was repeated 9 times under the same conditions, and the 10 th reaction result was recorded. The evaluation results are shown in Table 2.
Example 6
The molecular sieve N1 obtained in preparation example 1 and 1, 2-butanediol are mixed according to a volume ratio of 1:50, are subjected to treatment for 5 hours at 30 ℃ and normal pressure, and are filtered to obtain the molecular sieve O6.
Mixing zirconium oxychloride with ethanol to obtain a 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 under 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 under reduced pressure to obtain molecular sieve solid, further drying at 120 ℃ for 12 hours, and roasting at 550 ℃ for 6 hours to obtain a heteroatom molecular sieve sample with zirconium-enriched surface, and the number is R6.
XRF and transmission electron microscopy spectra characterization was performed on R6 and the results are shown in table 1.
Evaluation of the reaction: r6 is mixed 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 mol 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, the liquid phase product is separated for chromatographic analysis. The catalyst was separated, the reaction was repeated 9 times under the same conditions, and the 10 th reaction result was recorded. The evaluation results are shown in Table 2.
Example 7
The molecular sieve N1 obtained in preparation example 1 and 1, 2-propylene glycol are mixed according to a volume ratio of 1:60, are subjected to treatment at 10 ℃ and normal pressure for 8 hours, and then are filtered to obtain the molecular sieve O7.
Zirconium nitrate and ethyl acetate are mixed to obtain a liquid P7 containing a zirconium source, wherein the mass fraction of the zirconium nitrate is 5%, and then the liquid P7 and the molecular sieve O7 are mixed and treated for 60 minutes under the conditions of 20 ℃ and normal pressure, wherein the mol ratio of zirconium element to the molecular sieve O7 (calculated as SiO 2) in the liquid P7 is 0.005:1. And (3) evaporating the solvent under reduced pressure to obtain molecular sieve solid, further drying at 140 ℃ for 12 hours, and roasting at 550 ℃ for 6 hours to obtain a heteroatom molecular sieve sample with zirconium-enriched surface, number R7.
XRF and transmission electron spectroscopy characterization was performed on R7 and the results are shown in table 1.
Evaluation of the reaction: r7 is mixed 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 mol 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, the liquid phase product is separated for chromatographic analysis. The catalyst was separated, the reaction was repeated 9 times under the same conditions, and the 10 th reaction result was recorded. The evaluation results are shown in Table 2.
Example 8
The molecular sieve N1 obtained in preparation example 1 and 1, 4-butanediol are mixed according to the volume ratio of 1:80, are subjected to treatment for 6 hours at 20 ℃ and normal pressure, and are filtered to obtain the molecular sieve O8.
Zirconium n-propoxide and acetone are mixed to obtain a liquid P8 containing a zirconium source, wherein the mass fraction of the zirconium n-propoxide is 25%, and then the liquid P8 and the molecular sieve O8 are mixed and treated for 120min under the conditions of 70 ℃ and normal pressure, wherein the molar ratio of zirconium element to the molecular sieve O8 (calculated as SiO 2) in the liquid P8 is 0.02:1. And (3) evaporating the solvent under reduced pressure to obtain molecular sieve solid, drying at 100 ℃ for 18h, and roasting at 600 ℃ for 6h to obtain a heteroatom molecular sieve sample with zirconium-enriched surface, wherein the number is R8.
XRF and transmission electron spectroscopy characterization was performed on R8 and the results are shown in table 1.
Evaluation of the reaction: r8 is mixed 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 mol 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, the liquid phase product is separated for chromatographic analysis. The catalyst was separated, the reaction was repeated 9 times under the same conditions, and the 10 th reaction result was recorded. The evaluation results are shown in Table 2.
Example 9
This example was used to prepare a surface zirconium-rich beta molecular sieve and to evaluate the reaction.
The molecular sieve N1 obtained in preparation example 1 is mixed with glycerin according to a volume ratio of 1:70, and the mixture is treated for 24 hours at 100 ℃ under normal pressure, and then the mixture is filtered to obtain molecular sieve O9.
Zirconium oxychloride is mixed with methanol to obtain liquid P9 containing a zirconium source, wherein the mass fraction of the zirconium oxychloride is 8%, and then the liquid P9 and the molecular sieve O9 are mixed and treated for 120min at 80 ℃ under normal pressure, wherein the mol ratio of zirconium element to the molecular sieve O9 (calculated as SiO 2) in the liquid P9 is 0.015:1. And (3) evaporating the solvent under reduced pressure to obtain molecular sieve solid, drying at 110 ℃ for 5 hours, and roasting at 550 ℃ for 6 hours to obtain a heteroatom molecular sieve sample with zirconium-enriched surface, and the number is R9.
XRF and transmission electron microscopy spectra characterization was performed on R9 and the results are shown in table 1.
Evaluation of the reaction: r9 is mixed 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 mol 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, the liquid phase product is separated for chromatographic analysis. The catalyst was separated, the reaction was repeated 9 times under the same conditions, and the 10 th reaction result was recorded. The evaluation results are shown in Table 2.
Example 10
This example was used to prepare a surface zirconium-rich beta molecular sieve and to evaluate the reaction.
The molecular sieve N1 obtained in preparation example 1 is mixed with a mixture of naphthalene diphenol and ethanol according to a volume ratio of 1:50, wherein the mass fraction of naphthalene diphenol in the mixture of naphthalene diphenol and ethanol is 50%, the mixture is treated for 12 hours at 30 ℃ under normal pressure, and then the mixture is filtered to obtain the molecular sieve O10.
Zirconium tetrachloride and butanol are mixed to obtain a liquid P10 containing a zirconium source, wherein the mass fraction of the zirconium tetrachloride is 25%, and then the liquid P10 and the molecular sieve O10 are mixed and treated for 240min under the conditions of 100 ℃ and normal pressure, wherein the molar ratio of zirconium element to the molecular sieve O10 (calculated as SiO 2) in the liquid P10 is 0.04:1. And (3) evaporating the solvent under reduced pressure to obtain molecular sieve solid, further drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 12 hours to obtain a heteroatom molecular sieve sample with zirconium-enriched surface, number R10.
XRF and transmission electron spectroscopy characterization was performed on R10 and the results are shown in table 1.
Evaluation of the reaction: r10 is mixed 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 mol 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, the liquid phase product is separated for chromatographic analysis. The catalyst was separated, the reaction was repeated 9 times under the same conditions, and the 10 th reaction result was recorded. The evaluation results are shown in Table 2.
Example 11
This example was used to prepare a surface zirconium-rich beta molecular sieve and to evaluate the reaction.
The difference from example 1 is that a zirconium-containing hetero atom molecular sieve R11 was prepared with the beta molecular sieve N2 obtained in preparation example 2, and the characterization and evaluation reactions were performed, and the results are shown in tables 1 and 2.
Comparative example 1
This comparative example is used to illustrate Zr-. Beta.molecular sieves hydrothermally synthesized and to evaluate the reaction.
Reference methods Zr-beta molecular sieves (RSC adv.,2014,4,13481-13489) were hydrothermally synthesized in a fluorine-containing system.
10.42g of tetraethyl silicate are weighed out, mixed with 10.31g of tetraethyl ammonium hydroxide (40 wt% aqueous solution) and hydrolyzed with stirring. After 2h, 1.55g of an aqueous solution of zirconium oxychloride was added, in a molar ratio of zirconium to silicon of 0.01:1. After stirring the resulting mixture for a further 8 hours, 1.215ml of HF solution (40 wt%) and 0.105g of pure silicon beta molecular sieve were added as seed crystals. Crystallizing the obtained mixture at 140 ℃ for 20 days, filtering and washing to obtain a solid product, drying the solid product at 120 ℃ for 12 hours, and roasting at 550 ℃ for 6 hours to obtain a Zr-beta molecular sieve comparative sample, and the number is D1.
XRF and transmission electron spectroscopy characterization was performed on D1, and the results are shown in table 1.
Evaluation of the reaction: and mixing D1 with levulinic acid and sec-butyl alcohol, wherein the weight ratio of the 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 separating a liquid phase product after the reaction is finished for chromatographic analysis. The catalyst was separated, the reaction was repeated 9 times under the same conditions, and the 10 th reaction result was recorded. The evaluation results are shown in Table 2.
Comparative example 2
This comparative example is used to illustrate Zr-. Beta.molecular sieves prepared by post-synthesis zirconium intercalation and to evaluate the reaction.
Zirconium oxychloride is mixed with ethanol 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 for 30min at 50 ℃ under normal pressure, wherein the mol ratio of zirconium element to the molecular sieve O1 (calculated as SiO 2) in the liquid P11 is 0.01:1. And then decompressing and evaporating the solvent to obtain molecular sieve solid, further drying the obtained molecular sieve solid at 120 ℃ for 12 hours, and roasting at 550 ℃ for 6 hours to obtain a Zr-beta molecular sieve comparative sample, and the number is D2.
XRF and transmission electron spectroscopy characterization was performed on D2, and the results are shown in table 1.
Evaluation of the reaction: d2 is mixed with levulinic acid and sec-butyl alcohol, wherein the weight ratio of the D2 molecular sieve to the levulinic acid is 0.05:1, the mol 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, the liquid phase product is separated for chromatographic analysis. The catalyst was separated, the reaction was repeated 9 times under the same conditions, and the 10 th reaction result was recorded. The evaluation results are shown in Table 2.
TABLE 1
Sample of Bulk Zr/Si (mol) (surface Zr/Si)/(center 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 molar ratio of zirconium to silicon on the surface of the Zr-beta molecular sieve provided by the invention is higher than that on the central part, the molar ratio of zirconium to silicon on the surface is between 10 and 86, and the molar ratio of zirconium to silicon on the central part is obviously higher than that of 0.8 and 1.2 in the prior art D1 and D2, and the Zr-beta molecular sieve has obvious surface zirconium-rich property.
TABLE 2
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 catalyst has higher raw material conversion rate and product yield, and compared with comparative example, the catalyst has higher 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 have been described in detail above with reference to the accompanying drawings, but the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, and all the simple modifications belong to the protection scope of the present disclosure.
In addition, the specific features described in the foregoing embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present disclosure does not further describe various possible combinations.
Moreover, any combination between the various embodiments of the present disclosure is possible as long as it does not depart from the spirit of the present disclosure, which should also be construed as the disclosure of the present disclosure.

Claims (15)

1. A zirconium-containing heteroatom molecular sieve having a BEA structure, the ratio of the molar ratio of zirconium to silicon at the surface site of the molecular sieve to the molar ratio of zirconium to silicon at the central site of the molecular sieve being (1.5-200): 1, the mol ratio of zirconium to silicon in the molecular sieve phase is (0.001-0.04): 1, a step of; 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 respectively determined by TEM energy spectrum characterization, and rectangular selective areas at the surface part of the molecular sieve and rectangular selective areas at the central part of the molecular sieve of TEM morphology pictures of the molecular sieve crystal grains are respectively selected as target points for composition analysis; wherein,,
the rectangular selective area of the molecular sieve surface part is that a tangent line is made on the boundary of the molecular sieve crystal grain, a region which is perpendicular to the tangent line and has a distance of less than 10nm is selected, the rectangular selective area falls in the region, and the overlapping area of the rectangular selective area and the molecular sieve crystal grain is 50-3000 nm 2 ；
The rectangular selective area at the center of the molecular sieve takes the grain boundary of the molecular sieve as the boundary of the largest inscribed circle and takes 50 percent of the radius of the inscribed circle as the concentric circle, the rectangular selective area is positioned in the concentric circle, and the area of the rectangular selective area is50～3000nm 2 。
2. A process for the preparation of a zirconium heteroatom containing molecular sieve according to claim 1 characterized in that the process comprises the steps of contacting a molecular sieve N having framework hydroxyl vacancies with a polyhydroxy compound and separating to obtain molecular sieve O, contacting molecular sieve O with a zirconium source containing liquid P and recovering the product.
3. The method for preparing the molecular sieve containing zirconium hetero atoms according to claim 2, wherein the skeleton hydroxyl vacancy refers to an infrared hydroxyl spectrum with a wave number of 3550cm -1 There are distinct characteristic peaks in the vicinity.
4. The method for preparing the molecular sieve containing zirconium hetero atoms according to claim 2, wherein the molecular sieve N with skeleton hydroxyl vacancies is a molecular sieve of which the silicon-aluminum molecular sieve is subjected to partial skeleton atom removal and the infrared hydroxyl spectrogram is 3735cm in wave number -1 Characteristic peak intensity and wavenumber in the vicinity of 3550cm -1 Ratio of nearby characteristic peak intensities I 3735 /I 3550 4 to 10.
5. The method for preparing a zirconium-containing heteroatom molecular sieve according to claim 2, characterized in that the polyhydroxy compound has a carbon number of 2 to 12 and a hydroxyl number of at least 2.
6. The method for preparing a zirconium-containing heteroatom molecular sieve according to claim 2, characterized in that the polyhydroxy compound is contacted with the molecular sieve N having skeleton hydroxyl vacancies in the form of a polyhydroxy compound-containing liquid, the mass fraction of the polyhydroxy compound in the liquid being 20 to 100%; the polyhydroxy compound-containing liquid contains a solvent for dissolving the polyhydroxy compound.
7. The method for preparing a molecular sieve containing zirconium hetero atoms according to claim 6, wherein the solvent in which the polyhydroxyl compound is dissolved is alcohol, ketone, ether, ester.
8. The method for preparing a molecular sieve containing zirconium hetero atoms according to claim 2, wherein the contacting treatment of the molecular sieve N with skeleton hydroxyl vacancies with the polyhydroxy compound is carried out at 5-100 ℃ and 0.01-5MPa, and the pressure is absolute.
9. The method for preparing the molecular sieve containing zirconium heteroatom according to claim 2, characterized in that the zirconium source is an organozirconium source and/or an inorganic zirconium source.
10. The method for preparing the zirconium-containing heteroatom molecular sieve according to claim 9, characterized in that the organic zirconium source is selected from zirconium n-propoxide, zirconium isopropoxide, zirconium n-butoxide, zirconocene dichloride, zirconium acetate, zirconium propionate, zirconium tetrabenzyl, zirconium tetra (ethylmethylamino) (IV), zirconium tetramethacrylate, zirconium hexafluoro-acetylacetonate, zirconium chlorodicyclopentadienyl, zirconium zirconate, zirconium acetylacetonate, zirconium bis (n-butylcyclopentadienyl) dichloride, cyclopentadienyl zirconium trichloride, zirconium tetra (dimethylamino) zirconium, zirconium 1, 1-trifluoroacetylacetonate, zirconium pentamethylcyclopentadienyl (IV) trichloride, zirconium tetraethoxide, zirconium tetra (2, 6-tetramethyl-3, 5-heptanedioic acid), zirconium bis (pentamethylcyclopentadienyl) dichloride, zirconium rac-ethylene bis (1-indenyl) dichloride, zirconium isooctanoate, zirconium dicyclopentadienyl dimethyl, zirconium bis (cyclopentadienyl) dihydride, zirconium tert-butoxide, zirconium bis (methylcyclopentadienyl) dichloride, bis [ carbon ] ammonium dichloride, bis (cyclopentadienyl) dicyclopentadiene (1-bis (methyl) zirconium) dichloride, bis (t-di (cyclopentadienyl) zirconium) dichloride, bis (methyl) zirconium (3-bis (cyclopentadienyl) dichloride, bis (methyl) zirconium (1-bis (3-butanediyl) 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.
11. The method for preparing a zirconium-containing heteroatom molecular sieve according to claim 2, characterized in that the zirconium source-containing liquid P comprises a solvent which can dissolve the zirconium source and is selected from alcohols, ketones, ethers, esters or water having a C1-C10.
12. The process for preparing a zirconium-containing heteroatom molecular sieve according to claim 2, characterized in that the contacting of the molecular sieve O with the zirconium source-containing liquid P is carried out at 5 to 100 ℃ and 0.01 to 5MPa under an absolute pressure.
13. The method for preparing a molecular sieve containing zirconium hetero atoms according to claim 2, wherein the recovering the product includes a step of evaporating the solvent at normal pressure or reduced pressure.
14. The method for preparing a molecular sieve containing zirconium hetero atoms according to claim 13, wherein the recovered product further includes a drying step under vacuum or normal pressure at a temperature of 60-200 ℃ and a roasting step under oxygen-deficient or oxygen-enriched conditions at 300-800 ℃.
15. A method for catalyzing MPV reaction, which is characterized in that under the MPV reaction condition, the zirconium-containing heteroatom molecular sieve as defined in claim 1 is used as a catalyst to catalyze ketone to react with secondary alcohol to generate corresponding alcohol and ketone.
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