CN113070096B - Biomass oxidative cracking catalyst based on modified H-Beta molecular sieve, and preparation method and application thereof - Google Patents
Biomass oxidative cracking catalyst based on modified H-Beta molecular sieve, and preparation method and application thereof Download PDFInfo
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- CN113070096B CN113070096B CN202110304059.XA CN202110304059A CN113070096B CN 113070096 B CN113070096 B CN 113070096B CN 202110304059 A CN202110304059 A CN 202110304059A CN 113070096 B CN113070096 B CN 113070096B
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- catalyst
- molecular sieve
- active component
- oxidative cracking
- biomass
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- 239000003054 catalyst Substances 0.000 title claims abstract description 107
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 33
- 238000005336 cracking Methods 0.000 title claims abstract description 32
- 239000002028 Biomass Substances 0.000 title claims abstract description 27
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 26
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 239000002243 precursor Substances 0.000 claims description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 24
- 239000001301 oxygen Substances 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- PWMWNFMRSKOCEY-UHFFFAOYSA-N 1-Phenyl-1,2-ethanediol Chemical compound OCC(O)C1=CC=CC=C1 PWMWNFMRSKOCEY-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 10
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- HEVMDQBCAHEHDY-UHFFFAOYSA-N (Dimethoxymethyl)benzene Chemical compound COC(OC)C1=CC=CC=C1 HEVMDQBCAHEHDY-UHFFFAOYSA-N 0.000 claims description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 7
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 claims description 5
- 229940095102 methyl benzoate Drugs 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 9
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 9
- 229910021645 metal ion Inorganic materials 0.000 abstract description 9
- 239000010457 zeolite Substances 0.000 abstract description 9
- 239000002841 Lewis acid Substances 0.000 abstract description 8
- 150000007517 lewis acids Chemical class 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 6
- 150000002009 diols Chemical group 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 230000008859 change Effects 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005342 ion exchange Methods 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 29
- 239000002253 acid Substances 0.000 description 18
- 239000010949 copper Substances 0.000 description 16
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- 150000000180 1,2-diols Chemical class 0.000 description 12
- 238000003795 desorption Methods 0.000 description 9
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- 239000011148 porous material Substances 0.000 description 8
- 239000005711 Benzoic acid Substances 0.000 description 7
- 235000010233 benzoic acid Nutrition 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 7
- 238000007248 oxidative elimination reaction Methods 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000011949 solid catalyst Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000001476 alcoholic effect Effects 0.000 description 4
- -1 aryl 1, 2-diol Chemical class 0.000 description 4
- HUMNYLRZRPPJDN-KWCOIAHCSA-N benzaldehyde Chemical group O=[11CH]C1=CC=CC=C1 HUMNYLRZRPPJDN-KWCOIAHCSA-N 0.000 description 4
- 229940095076 benzaldehyde Drugs 0.000 description 4
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- 229910002480 Cu-O Inorganic materials 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- CRZQGDNQQAALAY-UHFFFAOYSA-N Methyl benzeneacetate Chemical compound COC(=O)CC1=CC=CC=C1 CRZQGDNQQAALAY-UHFFFAOYSA-N 0.000 description 2
- 229910003849 O-Si Inorganic materials 0.000 description 2
- 229910003872 O—Si Inorganic materials 0.000 description 2
- 206010048669 Terminal state Diseases 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
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- 238000012512 characterization method Methods 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
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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
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
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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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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
- C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
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Abstract
The invention discloses a biomass organic molecule oxidative cracking catalyst based on a modified H-Beta molecular sieve, a preparation method and an application thereof, wherein a metal component with better catalytic activity to vicinal diol is selected to carry out ion exchange with dealuminized H-Beta zeolite, so that the active component enters a framework of a dealuminized molecular sieve to be used as a Lewis acid and an adsorption site in a reaction process, the valence change of the metal ion and the synergistic action of the metal ion and an H-Beta carrier are further utilized to effectively improve the cracking activity and the reaction selectivity, and the efficient and reusable catalyst meeting the requirement of the breakage of the C-C bond of the vicinal diol is constructed. The catalyst prepared by the invention is used for the benzene-based glycol oxidative cracking reaction, the conversion rate of the benzene-based glycol is high, the yield of the oxidative cracking product reaches over 95 percent, and the catalyst has unique advantages in the biomass organic molecule oxidative cracking reaction.
Description
Technical Field
The invention relates to the field of biomass chemical conversion and utilization, in particular to a biomass oxidative cracking catalyst based on a modified H-Beta molecular sieve, and a preparation method and application thereof.
Background
Biomass is the most widely occurring substance on earth, and the main components, lignin and cellulose, are regenerated at a rate of about 1640 million tons per year, which corresponds to 15-20 times the oil production, e.g., in terms of energy. Meanwhile, biomass is a clean renewable resource with a wider source than fossil resources because it is carbon neutral.
In many biomass constituent monomers, a structure containing hydroxyl groups on two or more adjacent carbon atoms is present, and the structure is similar to a structural unit such as 1, 2-diol. Thus, many biomass conversions can be analytically discussed starting from the changes in the 1, 2-diol building blocks. If the selective oxidation of 1, 2-diol can be realized under mild conditions, and the C-C bond of the vicinal diol is broken to generate corresponding aldehyde or ketone, so that the biomass is converted into a high value-added product of small molecules, the utilization of the biomass is deeply influenced.
Chinese patent application No. 201110032160.0 discloses an oxidation process for breaking the alcoholic hydroxyl group of an aryl 1, 2-diol by breaking the C-C bond to a ketone. The process converts 2-methyl-1-phenyl-1, 2-propanediol, alpha- (1-hydroxycyclohexyl) -benzene-methanol, 1- (4-methoxyphenyl) -2-methyl-1, 2-propanediol to the corresponding ketone using liquid bromine as the oxidizing agent. The oxidant achieves high conversion and high selectivity of the aryl 1, 2-diol. However, liquid bromine is easy to volatilize and has strong toxicity and corrosivity, so that the liquid bromine cannot meet the requirement of clean production. Meanwhile, since liquid bromine is a homogeneous phase oxidant, the liquid bromine is difficult to separate from a reaction system and is difficult to recover and reuse.
The publication Coordination Chemistry Reviews,2015,301-302:147-162 reports that oxidative cleavage of 1, 2-diols such as hydrobenzoin, phenylglycol and the like is achieved by using a homogeneous vanadium-based polyoxometalate as a catalyst using oxygen as a cleaning oxidant, and the C-C bond of the 1, 2-diol is cleaved and the alcoholic hydroxyl group is converted into the corresponding aldehyde or ester. The method uses O2As a clean oxidant, the use of toxic and harmful oxidants is avoided. Published Journal of Molecular Catalysis A Chemical,1996,110(3) 221-226; journal of Molecular Catalysis A Chemical,2006,243(2) 214-; organic Letters,1999,1(5): 713-715; journal of Molecular Catalysis A Chemical,2000,156(1) 279-281; the Journal of Organic Chemistry,2010,75(7): 2321-2326; advanced Synthesis&Catalysis,2002,344(9), 1017-; catalysis Communications,2008,9(6): 1282-1285; a large number of homogeneous catalytic systems using O2 as the oxidizing agent were explored by Journal of the American Chemical Society,1988,110(4): 1187-. However, these homogeneous catalysts have no reusability and have low product selectivity.
Therefore, it becomes a difficult point to overcome to construct a new catalytic system with high reactivity and selectivity and excellent repeated use performance.
Disclosure of Invention
In order to solve the technical problems, the invention provides a biomass oxidative cracking catalyst based on a modified H-Beta molecular sieve, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a biomass oxidative cracking catalyst based on a modified H-Beta molecular sieve comprises the steps of dissolving an active component precursor in deionized water to obtain an active component solution, dispersing a dealuminized H-Beta molecular sieve in the active component solution, stirring and dipping, and performing rotary evaporation, drying and roasting to obtain the biomass oxidative cracking catalyst based on the modified H-Beta molecular sieve.
The invention is further improved in that the precursor of the active component is copper salt, zinc salt, iron salt, cobalt salt, silver salt or auric acid.
The invention has the further improvement that the active component precursor is one or more of copper nitrate, copper sulfate, copper chloride, zinc nitrate, zinc sulfate, zinc chloride, ferric nitrate, ferrous nitrate, ferric sulfate, ferrous sulfate, ferric chloride, ferrous chloride, silver nitrate, cobalt chloride, cobalt sulfate, cobalt nitrate and tetrachloroauric acid;
the invention further improves that the mass ratio of the active component precursor to the dealuminized H-Beta molecular sieve is (0.01-1): 1.
The invention has the further improvement that the stirring and dipping speed is 300-500 r/min, and the stirring and dipping time is 1-48 h; the temperature of the rotary evaporation is 40-80 ℃, the pressure is 10-80 kPa, and the rotating speed is 10-80 r/min.
The invention has the further improvement that the drying temperature is 80-150 ℃, and the drying time is 2-12 h.
The invention is further improved in that the specific roasting conditions are as follows: heating the mixture from room temperature to 300-600 ℃ at a heating rate of 2 ℃/min, and preserving the heat for 4-6 h.
The biomass oxidative cracking catalyst based on the modified H-Beta molecular sieve prepared by the method has the surface Lewis acid content of 200-800 mu mol (NH)3)/g，
The acid content is 100 to 500 [ mu ] mol (NH)3) (NH) in a total acid amount of 800 to 1500. mu. mol/g3) The specific surface area of the catalyst is 200-600 m2The grain size of the catalyst is 50-800 nm, and the pore volume of the catalyst is 0.1-1.0 mL/g.
The application of the biomass oxidative cracking catalyst based on the modified H-Beta molecular sieve prepared by the method comprises the steps of dissolving phenyl ethylene glycol in a solvent, adding the solvent into a high-pressure reaction kettle, adding the catalyst, pressurizing to 0.5-5 MPa through oxygen, and reacting for 2-24 hours at 100-200 ℃ to obtain an oxidative cracking product.
The invention is further improved in that the solvent is one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol and tetrahydrofuran; the mass ratio of the phenyl glycol to the catalyst is 1: (0.05-0.5).
The further improvement of the invention is that the drying temperature is 80-150 ℃, the drying time is 1-6 h, and the specific roasting conditions are as follows: heating the mixture from room temperature to 300-600 ℃ at a heating rate of 5-20 ℃/min, and keeping the temperature for 0.5-3 h.
Compared with the prior art, the invention has the following beneficial effects:
the H-Beta zeolite selected by the invention is a solid material which is porous, has a regular structure and mechanical and chemical stability, and can be used as a carrier of heterogeneous reaction. The H-Beta zeolite has a three-dimensional twelve-membered ring pore structure, which not only enables the H-Beta zeolite to have larger specific surface area and thermal stability, but also has excellent ion exchange performance, namely, the dealuminated H-Beta zeolite allows a metal precursor to be filled into a vacancy left by etching aluminum. Based on the method, a metal component with better catalytic activity to the vicinal diol can be selected to perform ion exchange with the dealuminized molecular sieve, and the metal component enters a framework of the dealuminized molecular sieve to serve as a Lewis acid and an adsorption site in a reaction process, so that the valence change of the metal ion and the synergistic action of the metal ion and an H-Beta carrier are utilized to adjust the cracking activity and the reaction selectivity, and thus, the efficient and reusable catalyst meeting the requirement of the breakage of the vicinal diol C-C bond is constructed, and a new economic, efficient and environment-friendly way is explored for the utilization of biomass with a 1, 2-diol structure. The dealuminized zeolite is adopted in the invention, so that the active component can enter into the vacant sites left by etching aluminum, and the activity of the catalyst is improved.
The invention discloses a catalyst based on a modified H-Beta molecular sieve, which is used for biomass oxidative cracking reaction, and is developed by taking a dealuminized H-Beta molecular sieve as a carrier, selecting metal with cracking activity as an active center, adopting an impregnation method, and performing rotary evaporation, drying, roasting and the like. In the process, active components enter a framework of the dealuminized molecular sieve by using the amount and preparation method of precursors of different active components under the condition of keeping the texture property of a catalyst carrier basically unchanged.
Hair brushCatalysts obtained as described above
The acid proton H can attack the alcoholic hydroxyl group on the 1, 2-diol, and a carbenium ion which is easily attacked by the nucleophilic group can be obtained after dehydration. On the other hand, the metal ions serving as strong Lewis acid sites can effectively adsorb oxygen, and the adsorbed oxygen can obtain electrons to achieve the balance of various oxygen species. And O having nucleophilicity therein2 2-And O2-The electron deficient carbenium ion can be attacked so that the C-C bond between the diols is broken and a carbon-oxygen double bond is formed. In addition, the metal ion sites of the active sites, after adsorption of oxygen molecules, break chemical bonds with lattice oxygen. O with nucleophilicity2-Inserted into the electron deficient position of the 1, 2-diol, the metal ion is reduced to a lower valence state. The low valence metal ion can give out electron and be oxidized to initial high valence by oxygen, to realize self circulation. When the chemical bond between the metal ion and the lattice oxygen is broken, the resulting lattice O is broken2-The ions also have the ability to attack electron deficient sites in the 1, 2-diol to effect oxidation of the reactants. After oxidation, oxygen defects may form in the catalyst due to the presence of O in the reaction system2Oxygen defects can be replenished by oxygen in the gas phase.
The catalyst has the advantages of simple preparation method, low raw material price, mild process conditions, green reaction process, reusability of the catalyst and the like, and has unique advantages in the biomass oxidative cracking reaction.
Furthermore, the slow heating rate of 2 ℃/min is adopted, so that the pore structure control of the dealuminized molecular sieve carrier is facilitated, and the fast heating rate can cause the pore structure change of the dealuminized H-Beta zeolite carrier.
Furthermore, the heat preservation is carried out for 4-6 hours at the temperature of 300-600 ℃ so as to enable the water-soluble precursor of the active component to generate a corresponding oxide and improve the activity of the catalyst.
The catalyst prepared by the invention is used for the reaction of biomass oxidative cracking, the conversion rate of a model reactant, namely phenyl ethylene glycol, is higher, the selectivity and the yield of an oxidative cracking product are higher, and the catalyst has recoverability.
Drawings
The invention is described in further detail below with reference to the attached drawings and the detailed description.
FIG. 1 is an X-ray diffraction pattern of the catalyst prepared in example 3.
Fig. 2 is an SEM image of the catalyst prepared in example 3. Wherein (a) is low magnification and (b) is high magnification.
FIG. 3 is a plot of NH3-TPD for the catalyst prepared in example 3.
Figure 4 is an XPS characterization of the catalyst prepared in example 3.
FIG. 5 is an X-ray diffraction pattern of the catalyst prepared in example 7.
Fig. 6 is an SEM image of the catalyst prepared in example 7. Wherein (a) is low magnification and (b) is high magnification.
FIG. 7 is an SEM photograph of the catalyst after the reaction of example 16. Wherein (a) is low magnification and (b) is high magnification.
FIG. 8 is an XPS characterization of the catalyst after the reaction of example 16 is complete.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention discloses a preparation method of a biomass oxidative cracking catalyst based on a modified H-Beta molecular sieve, which comprises the following steps:
dissolving a soluble active component precursor in deionized water to obtain an active component solution, then dispersing a dealuminized H-Beta carrier in the active component solution, stirring and dipping, and carrying out rotary evaporation, drying and roasting to obtain the heterogeneous supported catalyst.
Wherein the soluble active component precursor is one or more of cupric nitrate, copper sulfate, cupric chloride, zinc nitrate, zinc sulfate, zinc chloride, ferric nitrate, ferrous nitrate, ferric sulfate, ferrous sulfate, ferric chloride, ferrous chloride, silver nitrate, cobalt chloride, cobalt sulfate, cobalt nitrate and tetrachloroauric acid.
The invention has the further improvement that the mass ratio of the active component precursor to the dealuminized H-Beta carrier is (0.01-1) to 1; stirring and dipping at the speed of 300-500 r/min for 1-48 h; the temperature of the rotary evaporation is 40-80 ℃, the pressure is 10-80 kPa, and the rotating speed is 10-80 r/min.
The further improvement of the invention is that the drying temperature is 80-150 ℃, the drying time is 2-12 h, and the specific roasting conditions are as follows: heating the mixture from room temperature to 300-600 ℃ at a heating rate of 2 ℃/min, and preserving the heat for 4-6 h.
The Lewis acid content on the surface of the biomass oxidative cracking catalyst can reach 200-800 mu mol (NH)3)/g，
The acid content is 100 to 500 [ mu ] mol (NH)3) (NH) in a total acid amount of 800 to 1500. mu. mol/g3) The specific surface area of the catalyst is 200-600 m2The grain size of the catalyst is 50-800 nm, and the pore volume of the catalyst is 0.1-1.0 mL/g.
An application of a biomass oxidative cracking catalyst based on a modified H-Beta molecular sieve in a phenyl ethylene glycol oxidative cracking reaction:
dissolving phenyl glycol in a certain amount of solvent, and then filling the solution and the catalyst into a high-pressure reaction kettle. Purging and replacing air in the high-pressure reaction kettle for 1-5 times by using oxygen, and pressurizing the oxygen to 0.5-5 MPa. And then transferring the reaction kettle to an intelligent constant-temperature timing magnetic stirrer, and stirring at the speed of 500-1200 r/min to start reaction after heating to the required reaction temperature. Obtaining an oxidative cracking product after the reaction is finished. And immersing the high-pressure reaction kettle into cold water at the temperature of 0-25 ℃ for rapid cooling, and separating the solid catalyst and the liquid product of oxidative cracking through centrifugal operation. The separated solid catalyst is dried and roasted to realize recovery.
The invention is further improved in that the solvent in the reaction process can be one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol and tetrahydrofuran.
The invention is further improved in that the mass ratio of the phenyl ethylene glycol to the catalyst is 1: (0.05-0.5).
The invention has the further improvement that the reaction temperature is 100-200 ℃, and the reaction time is 2-24 h.
The invention is further improved in that the rotating speed of centrifugal separation is 3000-10000 r/min.
In a further improvement of the invention, the liquid product may be one or more of benzaldehyde, benzyl alcohol, benzoic acid, methyl benzoate, ethyl benzoate and benzaldehyde dimethyl acetal.
The further improvement of the invention is that the drying temperature of the recovered solid catalyst is 80-150 ℃, the drying time is 1-6 h, and the specific roasting conditions are as follows: heating the mixture from room temperature to 300-600 ℃ at a heating rate of 1-10 ℃/min, and keeping the temperature for 0.5-3 h.
The following are specific examples.
Example 1
Dissolving an active component precursor in 30mL of deionized water to obtain an active component solution, then dispersing 4g of dealuminized H-Beta carrier in the active component solution, soaking for 12H under magnetic stirring at 400r/min, then rotationally evaporating the obtained suspension on a rotary evaporator at the temperature of 60 ℃ and the pressure of-0.09 MPa at the rotating speed of 40r/min to dryness, and drying the obtained solid in an oven at the temperature of 110 ℃ for 12H. After drying, placing the mixture in a muffle furnace, heating the mixture from room temperature to 450 ℃ at the heating rate of 2 ℃/min, and roasting the mixture for 6 hours to obtain the supported catalyst A. Wherein the active component precursor is Cu (NO)3)2·3H2O, the mass ratio of the active component precursor to the dealuminized H-Beta carrier is 5: 100;
example 2
The difference from the example 1 is that the mass ratio of the active component precursor to the dealuminized H-Beta carrier is 10: 100; the catalyst prepared in this example is designated B.
Example 3
The difference from the example 1 is that the mass ratio of the active component precursor to the dealuminized H-Beta carrier is 15: 100; the catalyst prepared in this example was designated C.
As can be seen in fig. 1, the X-ray diffraction pattern of catalyst C prepared in example 3 showed peak positions of 7.77 °, 11.39 °, 13.47 °, 14.70 °, 21.66 °, 22.55 °, 25.45 °, 27.14 °, 28.84 °, 29.72 °, 33.63 ° and 43.68 °, corresponding to the Beta molecular sieve topology, indicating that the texture properties of the modified catalyst support were essentially unchanged. The expansion of the zeolite framework structure is manifested as a change in the position of the main diffraction peak at diffraction angles 2 θ in the vicinity of 22.55 °. After modification, the 2 θ value of the main diffraction peak was reduced from 22.60 ° to 22.55 °, indicating that the zeolite Beta structure was expanded and the metal had entered the lattice.
As can be seen from (a) and (b) of fig. 2, the catalyst prepared in example 3 had a regularly grown spherical structure with a particle size of about 500 nm.
As can be seen from fig. 3, the catalyst prepared in example 3 has three distinct desorption peaks at different temperatures in the NH3-TPD desorption curve, and the temperatures of the desorption peaks correspond to the intensities of different surface acidity, indicating that the surface of the sample has acid centers with different intensities. The desorption (weak adsorption sites) at 100-250 ℃ can be attributed to the desorption of weakly adsorbed ammonia. The desorption band (moderate strength adsorption sites) occurring at 250-500 ℃ can be attributed to NH3 adsorbed on strong Lewis acid sites. Whereas the desorption (strong adsorption sites) above 550 ℃ can be attributed to adsorption
NH3 at the acid position. The area of the desorption peak corresponds to the number of acid sites under the corresponding acid strength, the amount of weak adsorption sites is 0.43mmol/g, the amount of medium-strength adsorption sites is 0.47mmol/g, the amount of strong adsorption sites is 0.24mmol/g, and the total acid amount is 1.14 mmol/g. The above results indicate that the catalyst surface has a certain amount of different strengths
Acid and Lewis acid acidic sites.
Acid sites can attack alcoholic hydroxyl groups on the 1, 2-diol, and carbocation which is easy to be attacked by nucleophilic groups is obtained after dehydration; the Lewis acid site can effectively adsorb oxygen and form oxygen species with nucleophilicity to attack the carbocation to realize the fracture of the C-C bond. Thus, the two acid sites may act synergistically to promote the cleavage of the C-C bond of the 1, 2-diol.
As can be seen from FIG. 4, in the Cu 2p spectrum, there are two peaks at 930-937 eV and 950-959 eV, which correspond to the Cu 2p3/2And Cu 2p1/2. In addition, two satellite-carried peaks appeared in the range 938-950 eV and 962-966 eV. As Cu (0) and 3d of Cu (I) are closed shells, only one final state appears; 3d of Cu (II) is an open shell layer, and 3d electrons can be overlapped and coupled with O2 p to generate terminal state splitting, so that two terminal states are generated, and a vibration-carrying satellite peak can be formed at the high binding energy position of a main peak. This therefore indicates the presence of Cu (II) in the catalyst prepared in example 3.
Adding Cu 2p3/2And Cu 2p1/2Deconvoluted into two peaks. The peaks at 952.5eV and 932.7eV indicate the presence of a Cu-O-Cu bond structure in the catalyst. While the Cu coordinated with the oxygen atom of the catalyst lattice is obtained at 953.4eV and 934.0eV of higher binding energy2+Peak, i.e., Cu-O-Si bond structure. Since Si is more electronegative than Cu, the Cu-O bond in Cu-O-Si has higher binding energy than the Cu-O bond in Cu-O-Cu. These results show that Cu2+And CuO were both present in the catalyst prepared in example 3 and both served as reactive sites, so that the C — C bond cleavage ability of the catalyst could be greatly increased.
Example 4
The difference from the example 1 is that the mass ratio of the active component precursor to the dealuminized H-Beta carrier is 20: 100; the catalyst prepared in this example was designated as D.
Example 5
The difference from the example 1 is that the mass ratio of the active component precursor to the dealuminized H-Beta carrier is 25: 100; the catalyst prepared in this example is designated as E.
Example 6
The difference from the example 1 is that the mass ratio of the active component precursor to the dealuminized H-Beta carrier is 50: 100; the catalyst prepared in this example is designated F.
Example 7
The difference from the example 1 is that the mass ratio of the active component precursor to the dealuminized H-Beta carrier is 100: 100; the catalyst prepared in this example was designated G.
As can be seen from FIG. 5, the X-ray diffraction pattern of the catalyst prepared in example 7 shows diffraction peaks corresponding to the topology of Beta molecular sieve. Meanwhile, diffraction peaks corresponding to the crystal form of copper oxide appeared at 35.52 °, 38.74 °, 48.77 °, 53.48 °, 58.31 ° and 61.65 °.
As can be seen from fig. 6 (a) and (b), the catalyst prepared in example 7 has a regularly grown spherical structure with a particle size of about 500 nm.
The specific surface areas, pore volumes, and mass fractions of active metals of the catalysts prepared in examples 1 to 7 are shown in Table 1.
TABLE 1 physicochemical Properties of the catalyst samples
Measuring BET specific surface area and pore volume by nitrogen physical adsorption and desorption tests;
b. the mass fraction of the active metal is calculated from the initial mixture ratio.
As can be seen from Table 1, the catalysts prepared in examples 1-7 all have larger specific surface area and pore volume, and can expose more active sites, which is beneficial for the catalytic reaction.
Example 8
The difference from example 1 is that the mass ratio of the active component precursor to the dealuminized H-Beta carrier is 1: 100.
Example 9
The difference from example 3 is that the active ingredient precursorIs CuCl2. The catalyst prepared in this example was designated as H.
Example 10
The difference from example 3 is that the active component precursor is Fe (NO)3)3. The catalyst prepared in this example is designated I.
Example 11
The difference from example 8 is that the active component precursor is Zn (NO)3)2. The catalyst prepared in this example is designated G.
Example 12
The difference from example 8 is that the active ingredient precursor is CoCl2. The catalyst prepared in this example is designated as K.
Example 13
The difference from example 8 is that the active ingredient precursor is tetrachloroauric acid. The catalyst prepared in this example was designated L.
Example 14
The same as example 1, except that the active component precursor was a mixture of copper nitrate and copper sulfate as in example 1.
Example 15
The difference from example 1 is that the active component precursor is a mixture of copper nitrate and copper chloride as in example 1.
The application of the supported catalyst in the benzene glycol oxidative cracking reaction comprises the following steps:
example 16
138mg of phenyl glycol was dissolved in 2mL of methanol to obtain a solution, and then the solution and 50mg of the catalyst in example 3 were charged into an autoclave. Purging and replacing air in the high-pressure reaction kettle for 3 times by using oxygen, and pressurizing the oxygen to 3.0 MPa. And then transferring the reaction kettle to an intelligent constant-temperature timing magnetic stirrer, controlling the reaction temperature to be 150 ℃, stirring at the speed of 800r/min, and reacting for 8 hours to obtain an oxidative cracking product.
And immersing the high-pressure reaction kettle in cold water at 4 ℃ for rapid cooling, and then separating out the solid catalyst from the obtained suspension by centrifugal operation at the rotating speed of 8000r/min to obtain four liquid-phase products of benzaldehyde, benzyl alcohol, methyl benzoate and benzaldehyde dimethyl acetal. And drying the separated solid catalyst at 120 ℃ for 2h, then heating from room temperature to 450 ℃ at the heating rate of 10 ℃/min, and preserving heat for 1h to realize the recovery of the catalyst.
As can be seen from (a) and (b) in fig. 7, the catalyst after the reaction is spherical particles having a particle size of about 500nm, and the structure and morphology thereof are substantially stable before and after the reaction.
As can be seen from FIG. 8, the catalyst after use only obtained two weak satellite-carrying peaks at the high binding energy of the main peak, which indicates that part of Cu changes from +2 valence to +1 valence during the reaction. This result confirmed that O having nucleophilicity is adsorbed on Cu during the reaction2-Species can be inserted into the position of electron deficiency in the 1, 2-diol, when the C-C bond of the reactant is broken, the Cu-O bond is broken, and the Cu can obtain electrons and be reduced to +1 valence.
Example 17
The difference from example 16 is that the solution and 50mg of the catalyst in example 1 were charged into an autoclave.
Example 18
The difference from example 16 is that the solution and 50mg of the catalyst in example 2 were charged into an autoclave.
Example 19
The difference from example 16 is that the solution and 50mg of the catalyst in example 4 were charged into an autoclave.
Example 20
The difference from example 16 is that the solution and 50mg of the catalyst in example 5 were charged into an autoclave.
Example 21
The difference from example 16 is that the solution and 50mg of the catalyst in example 6 were charged into an autoclave.
Example 22
The difference from example 16 is that the solution and 50mg of the catalyst in example 7 were charged into an autoclave.
The yields of the individual products and the total yield of the oxidative cleavage products in examples 17 to 22 are shown in Table 2.
TABLE 2 evaluation of catalyst Performance
Example 23
The difference from example 16 is that the catalyst of example 9 was used. The obtained products are benzaldehyde, benzyl alcohol, methyl benzoate and benzaldehyde dimethyl acetal.
Example 24
The difference from example 16 is that the catalyst in example 10 was used. The obtained product is benzaldehyde, benzyl alcohol, benzoic acid, methyl benzoate and 2-methoxy-2-phenyl-ethyl acetate.
Example 25
The difference from example 16 is that the catalyst in example 11 was used and the reaction temperature was controlled to 120 ℃. The obtained product is benzaldehyde and benzaldehyde dimethyl acetal.
Example 26
The difference from example 16 is that the catalyst in example 12 was used and the reaction temperature was controlled to 120 ℃. The obtained products are benzaldehyde dimethyl acetal and methyl phenylacetate.
Example 27
The difference from example 16 is that the catalyst in example 13 was used, and the reaction temperature was controlled to 120 ℃. The product obtained is benzaldehyde dimethyl acetal.
The yields of the respective products and the total yield of the oxidative cleavage products in examples 23 to 27 are shown in Table 3.
TABLE 3 evaluation of catalyst Properties
Example 28
The difference from example 16 is that the amount of catalyst used is 10 mg.
Example 29
The difference from example 16 is that the amount of catalyst used is 20 mg.
Example 30
The difference from example 16 is that the amount of catalyst used is 30 mg.
Example 31
The difference from example 16 is that the amount of catalyst used is 40 mg.
The yields of the individual products and the overall yields of the oxidative cleavage products in examples 28 to 31 are shown in Table 4.
TABLE 4 evaluation of catalyst Properties
Example 32
The difference from example 16 is that the solution and 6.9mg of the catalyst in example 1 were charged into an autoclave.
Example 33
The difference from example 16 is that the solution and 69mg of the catalyst in example 1 were charged into an autoclave.
Example 34
The difference from example 16 is that oxygen was pressurized to 0.5 MPa.
Example 35
The difference from example 16 is that oxygen was pressurized to 1.0 MPa.
Example 36
The difference from example 16 is that oxygen was pressurized to 2.0 MPa.
The yields of the respective products and the total yield of the oxidative cleavage products in examples 34 to 36 are shown in Table 5.
TABLE 5 evaluation of catalyst Properties
Example 37
The difference from example 16 is that oxygen was pressurized to 4 MPa.
Example 38
The difference from example 16 is that oxygen was pressurized to 5 MPa.
Example 39
The difference from example 16 is that the reaction temperature was controlled to 120 ℃.
Example 40
The difference from example 16 is that the reaction temperature was controlled to 130 ℃.
EXAMPLE 41
The difference from example 16 is that the reaction temperature was controlled to 140 ℃.
The yields of the respective products and the total yield of the oxidative cleavage products in examples 39 to 41 are shown in Table 6.
TABLE 6 evaluation of catalyst Properties
Example 42
The difference from example 16 is that the reaction temperature is controlled at 100 ℃ and the reaction time is 24 hours.
Example 43
The difference from example 16 is that the reaction temperature was controlled at 200 ℃ and the reaction time was 2 hours.
Example 44
The difference from example 16 is that the reaction temperature is controlled at 170 ℃ and the reaction time is 10 h.
Example 45
The difference from example 16 is that the reaction temperature is controlled at 160 ℃ and the reaction time is 20 hours.
Example 46
The difference from example 16 is that 138mg of styrene glycol was dissolved in 2mL of ethanol. The obtained product is benzaldehyde, benzyl alcohol, benzoic acid, ethyl benzoate and 2-methyl-4-phenyl-1, 3-dioxolane.
Example 47
The difference from example 16 is that 138mg of styrene glycol was dissolved in 2mL of n-propanol. The obtained product is benzaldehyde, benzyl alcohol, benzoic acid, and propyl benzoate.
Example 48
The difference from example 16 is that 138mg of styrene glycol was dissolved in 2mL of isopropanol. The obtained products are benzaldehyde, benzyl alcohol and benzoic acid.
Example 49
The difference from example 16 is that 138mg of phenylethanediol was dissolved in 2mL of n-butanol. The obtained products are benzaldehyde, benzyl alcohol and benzoic acid.
Example 50
The difference from example 16 is that 138mg of styrene glycol was dissolved in 2mL of tetrahydrofuran. The product obtained is benzoic acid.
The yields of the individual products and the overall yields of the oxidative cleavage products in examples 16, 46 to 50 are shown in Table 7.
TABLE 7 evaluation of catalyst Properties
In the invention, active components are introduced into a skeleton of dealuminized H-Beta to serve as active sites, and modified materials are utilized
The acid synergistic effect of the acid and the Lewis and the valence change of the active component in the reaction effectively improve the capability of the catalyst for breaking the C-C bond of the organic molecule of the biomass.
The above-mentioned embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (7)
1. The application of the biomass oxidative cracking catalyst based on the modified H-Beta molecular sieve is characterized in that: dissolving phenyl ethylene glycol in a solvent, adding the solution into a high-pressure reaction kettle, adding a catalyst, pressurizing to 0.5-5 MPa by using oxygen, and reacting at 100-200 ℃ for 2-24 h to obtain an oxidative cracking product, wherein the oxidative cracking product comprises one or more of benzaldehyde, benzyl alcohol, methyl benzoate and benzaldehyde dimethyl acetal;
the catalyst is prepared by the following method:
dissolving an active component precursor in deionized water to obtain an active component solution, then dispersing a dealuminized H-Beta molecular sieve in the active component solution, stirring and dipping, and performing rotary evaporation, drying and roasting to obtain a biomass oxidative cracking catalyst based on the modified H-Beta molecular sieve; wherein the stirring and dipping speed is 300-500 r/min, and the stirring and dipping time is 1-48 h;
the active component precursor is one or more of cupric nitrate, cupric sulfate, cupric chloride, ferric nitrate, ferrous nitrate, ferric sulfate, ferrous sulfate, ferric chloride and ferrous chloride.
2. Use according to claim 1, characterized in that: the solvent is one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol and tetrahydrofuran; the mass ratio of the phenyl glycol to the catalyst is 1: (0.05-0.5).
3. Use according to claim 1, characterized in that: the catalyst can be recycled and reused by drying and roasting; wherein the drying temperature is 80-150 ℃, the drying time is 1-6 h, and the specific roasting conditions are as follows: heating the mixture from room temperature to 300-600 ℃ at a heating rate of 5-20 ℃/min, and keeping the temperature for 0.5-3 h.
4. Use according to claim 1, characterized in that: the mass ratio of the active component precursor to the dealuminized H-Beta molecular sieve is (0.01-1) to 1.
5. Use according to claim 1, characterized in that: the temperature of the rotary evaporation is 40-80 ℃, the pressure is 10-80 kPa, and the rotating speed is 10-80 r/min.
6. Use according to claim 1, characterized in that: the drying temperature is 80-150 ℃, and the drying time is 2-12 h.
7. Use according to claim 1, characterized in that: the specific conditions of roasting are as follows: heating the mixture from room temperature to 300-600 ℃ at a heating rate of 2 ℃/min, and preserving the heat for 4-6 h.
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