CN117899891A - Catalyst for preparing benzaldehyde by oxidizing benzyl alcohol with oxygen under solvent-free condition, and preparation method and application thereof - Google Patents
Catalyst for preparing benzaldehyde by oxidizing benzyl alcohol with oxygen under solvent-free condition, and preparation method and application thereof Download PDFInfo
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- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 title claims abstract description 201
- 239000003054 catalyst Substances 0.000 title claims abstract description 138
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 235000019445 benzyl alcohol Nutrition 0.000 title claims abstract description 67
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 title claims abstract description 61
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000001301 oxygen Substances 0.000 title claims abstract description 37
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 37
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims abstract description 3
- 239000012265 solid product Substances 0.000 claims abstract description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 238000004817 gas chromatography Methods 0.000 claims description 12
- 239000011949 solid catalyst Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 10
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical group [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000012695 Ce precursor Substances 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 18
- 229910000510 noble metal Inorganic materials 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000000975 co-precipitation Methods 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 238000003837 high-temperature calcination Methods 0.000 abstract 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract 1
- 150000004706 metal oxides Chemical class 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 56
- 238000007254 oxidation reaction Methods 0.000 description 17
- 230000003647 oxidation Effects 0.000 description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 13
- 239000000706 filtrate Substances 0.000 description 10
- 238000005119 centrifugation Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- -1 each 1.2mmol) Substances 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 238000010792 warming Methods 0.000 description 9
- 102000020897 Formins Human genes 0.000 description 8
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- 239000000203 mixture Substances 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 7
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 230000007613 environmental effect Effects 0.000 description 2
- 238000010812 external standard method Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- 239000003205 fragrance Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a catalyst for preparing benzaldehyde by oxidizing benzyl alcohol with oxygen under a solvent-free condition, and a preparation method and application thereof. The method comprises the following steps: 1. Fe(NO)3·9H2O、Co(OAc)2、Ni(OAc)2·4H2O、Cr(OAc)3、Mn(OAc)2·4H2O is dissolved in deionized water, fully stirred, a certain amount of Ce (OAc) 3 and surfactant are added, and stirred for 12 hours at 60 ℃;2. adding ammonia water, continuously stirring for 12 hours, collecting a solid product, and drying in an oven; 3. placing the solid in a muffle furnace, and calcining for a certain time at a certain temperature to obtain the catalyst. The invention takes non-noble metal as a precursor, and prepares the composite metal oxide catalyst by coprecipitation and high temperature calcination. The preparation method disclosed by the patent is simple in process and low in cost. In addition, the obtained catalyst can be applied to the reaction of oxidizing benzyl alcohol to prepare benzaldehyde by oxygen under the condition of no solvent, so that excellent catalytic activity can be obtained. The catalyst is circularly regenerated after being washed and dried through centrifugal separation, and has good industrial application potential.
Description
Technical Field
The invention belongs to the field of catalyst preparation and application, and particularly relates to a preparation method and application of a catalyst for preparing benzaldehyde by oxidizing benzyl alcohol with oxygen under a solvent-free condition.
Background
The selective oxidation of benzyl alcohol to produce benzaldehyde is one of the most valuable reactions in organic synthesis and industrial catalysis, and is widely applied to the fields of medicines, pesticides, fragrances and the like because benzaldehyde is an important chemical intermediate. In industry, toluene is used as a raw material for producing benzaldehyde, and the benzaldehyde is prepared through the processes of chlorination-hydrolysis and the like of a side chain of the benzaldehyde, and the method is complex in process, serious in equipment corrosion and high in environmental protection pressure. Thus, the production of benzaldehyde by selective oxidation from benzyl alcohol as a raw material has attracted increasing attention. Traditionally, the reaction is often carried out in organic solvents (e.g., toluene, acetonitrile, benzotrifluoride) and expensive stoichiometric oxidants (e.g., periodic acid, permanganate, organic peroxides) are used, which not only increases production costs but also places pressure on environmental protection. Therefore, molecular oxygen is used as an oxidant, and the catalytic oxidation of benzyl alcohol to prepare benzaldehyde under the condition of no solvent has wide application potential.
Noble metal catalysts, such as Pd, au, etc., have been reported to be effective in catalyzing benzyl alcohol selective oxidation reactions, with Pd-based catalysts being the most widely used. For example, patent CN114904556a discloses a graphite-phase carbon nitride (g-C 3N4) supported Pd catalyst and is applied to benzyl alcohol solvent-free catalytic oxidation, pdCl 2 being prepared by impregnation and NaBH 4 reduction. Patent CN108772087a reports an aza-ordered mesoporous carbon supported Pd catalyst, in which the support is prepared in aqueous phase using a soft template, and Pd is supported on the support by impregnation reduction. While Pd-based catalysts can achieve good catalytic results, the high price and scarce reserves limit large-scale applications. For this reason, some non-noble metal catalysts are also used in the solvent-free catalytic oxidation of benzyl alcohol to prepare benzaldehyde, but their catalytic activity and catalyst cycle stability are still further improved. Therefore, the development of stable and efficient non-noble metal catalysts has great significance and economic value.
Overall, over the years of development, there are still several common problems in this reaction: first, in terms of oxidizing agents, many reaction systems use high-valence metal salts, organic peroxides, hydrogen peroxide, etc. as oxidizing agents, so that the cost increases and the explosion risk increases. Secondly, when oxygen is used as an oxidant, substrate benzyl alcohol and a catalyst are often dispersed in an organic solvent, and the introduction of the organic solvent increases the cost and the separation difficulty of benzaldehyde, and meanwhile, the method does not meet the development requirement of green chemistry. Finally, noble metal catalysts are still adopted in a plurality of oxidation systems, which adds a plurality of difficulties to the subsequent industrial production.
Disclosure of Invention
In order to solve the problems, the invention provides a catalyst for preparing benzaldehyde by oxidizing benzyl alcohol with oxygen under the condition of no solvent, and a preparation method and application thereof. Based on the catalyst, under the condition of no solvent, oxygen is used as an oxidant, the benzaldehyde can be prepared by selectively oxidizing benzyl alcohol to obtain excellent catalytic effect, and the catalyst can be recycled after simple centrifugal separation, so that the catalyst has excellent application prospect.
The catalyst disclosed by the invention is a cerium doped high-entropy oxide catalyst, wherein the high-entropy oxide is (FeCoNiCrMn) 3O4, and the preparation method comprises the following specific steps of:
Step1, dissolving a certain amount Fe(NO)3·9H2O、Co(OAc)2、Ni(OAc)2·4H2O、Cr(OAc)3、Mn(OAc)2·4H2O in deionized water, fully stirring, adding a certain amount Ce (OAc) 3 and a surfactant (cetyl trimethyl ammonium bromide), and stirring at 60 ℃ for 12 hours.
Step2, adding a proper amount of ammonia water (wt.28%), stirring for 12 hours, collecting a solid product and drying in an oven.
And step 3, placing the solid in a muffle furnace, and calcining for a specific time at a certain temperature to obtain the catalyst.
As a limitation of the present invention, in step 1 of the preparation method, ce: fe: co: ni: cr: the mole ratio of Mn metal precursor is (0.2-5): 1:1:1:1: the molar ratio of the Ce metal precursor to the surfactant is 1: (0.5-5).
In step 2, the dosage ratio of the Ce precursor to ammonia (wt.28%) is 1mmol: (1-20) mL.
In the step 3, the calcination temperature is 600-1000 ℃ and the calcination time is 2-8 h.
The catalyst obtained by the method is applied to the reaction for preparing benzaldehyde by selectively oxidizing benzyl alcohol under the condition of no solvent (oxygen is taken as an oxidant). The application method comprises the following steps: and (3) placing benzyl alcohol in a high-pressure reaction kettle with a quartz lining, filling oxygen (2 MPa), fully stirring, adding the catalyst, reacting for a certain time at a specific temperature, centrifugally separating the solid catalyst and the reaction liquid, and quantifying the reaction liquid by a gas chromatography external standard method.
In the application process, the reaction temperature is 80-200 ℃, preferably 150 ℃; the reaction time is 2 to 10 hours, preferably 5 hours.
In the application process, the ratio of the mass of the catalyst to the molar quantity of the benzyl alcohol is (0.5-10) mg:1mmol, preferably (1 to 5) mg:1mmol.
Through the technical scheme, compared with the prior art, the invention has the following beneficial effects:
The catalyst takes non-noble metal as a main active component, no noble metal is added, the cost is low, and the preparation process of the catalyst is simple. (FeCoNiCrMn) 3O4 has a stable high-entropy structure, so that the catalyst can keep stable structure before and after reaction, cerium doping is beneficial to generation of oxygen vacancies, adsorption and activation of the catalyst to O 2 are promoted, and the catalyst shows excellent catalytic activity in solvent-free catalytic oxidation of benzyl alcohol. In addition, the application method provided by the invention has low production cost and good industrialized application potential.
Drawings
FIG. 1 is an X-ray diffraction pattern of the catalyst obtained by the method described in example 2.
FIG. 2 is a scanning electron micrograph (a) and a transmission electron micrograph (b) of the catalyst obtained by the method described in example 5.
Detailed Description
The invention will be further illustrated with reference to the following examples. It is to be understood that these examples are intended to illustrate the invention and are not intended to limit the scope of the invention, which is not to be so limited.
It is worth mentioning that after the solid catalyst is separated, the filtrate is diluted by ethanol, analyzed by gas chromatography and quantified by an external standard method.
The chromatographic conditions were: fullenii chromatography (FuLi 9790 II), capillary column (PB-50, 30 mX0.32 mm X0.33 μm), hydrogen Flame Ionization Detector (FID); nitrogen was used as carrier gas, the sample inlet was 300 ℃, the detector was 300 ℃, the column was warmed up by programming from 50 ℃ to 200 ℃ at a rate of 10 ℃ min -1, and held for 1min. Wherein, the benzyl alcohol conversion rate and the benzaldehyde selectivity are calculated by the following formulas:
specific examples and comparisons of the invention are as follows:
example 1
Five metal precursors, each 1.2mmol),Fe(NO)3·9H2O(0.485g)、Co(OAc)2(0.212g)、Ni(OAc)2·4H2O(0.298g)、Cr(OAc)3(0.275g) and Mn (OAc) 2·4H2 O (0.294 g), were dissolved in 60mL of deionized water, 1.8 mmole Ce (OAc) 3 (0.570 g) was added with continuous stirring, then 2.6 mmole cetyltrimethylammonium bromide (CTAB) was added, the solution was warmed to 60 ℃, stirred for 12h, then 6.0mL of aqueous ammonia (28 wt.%) was added to the solution, and stirring was continued for 12h, the resulting precipitate was isolated by filtration, washed thoroughly with deionized water and ethanol, dried in an oven at 120 ℃ for 4h, the solid catalyst was collected in a crucible, calcined at 900 ℃ for 4h (the warming rate was 5 ℃ for min -1), and finally the target catalyst was obtained.
The target catalyst obtained in the example 1 is applied to the reaction of preparing benzaldehyde by oxidizing benzyl alcohol with oxygen under the condition of no solvent. 19.2mmol of benzyl alcohol, 50mg of catalyst and then oxygen (2.0 MPa) were added in this order to the autoclave, and the mixture was reacted at 150℃for 5 hours. After the reaction, the catalyst was separated by centrifugation, and the filtrate was diluted with ethanol and analyzed by gas chromatography, and the conversion of benzyl alcohol was calculated to be 37.7% and the selectivity of benzaldehyde was 87.6%.
In addition, the catalyst is centrifugally separated, and the recovered catalyst is washed with ethanol and water successively and dried for use. Under the same reaction conditions, the stability of the catalyst for preparing benzaldehyde by catalytic oxidation of benzyl alcohol is investigated, and the catalyst is circulated. The seventh recovered catalyst in this reaction gave a conversion of 37.2% of benzyl alcohol and a selectivity of 87.4% of benzaldehyde.
Example 2
Five metal precursors, each 1.2mmol),Fe(NO)3·9H2O(0.485g)、Co(OAc)2(0.212g)、Ni(OAc)2·4H2O(0.298g)、Cr(OAc)3(0.275g) and Mn (OAc) 2·4H2 O (0.294 g), were dissolved in 60mL of deionized water, 1.2 mmole Ce (OAc) 3 (0.380 g) was added with continuous stirring, then 2.6 mmole cetyltrimethylammonium bromide (CTAB) was added, the solution was warmed to 60 ℃, stirred for 12h, then 6.0mL of aqueous ammonia (28 wt.%) was added to the solution, and stirring was continued for 12h, the resulting precipitate was isolated by filtration, washed thoroughly with deionized water and ethanol, dried in an oven at 120 ℃ for 4h, the solid catalyst was collected in a crucible, calcined at 900 ℃ for 4h (the warming rate was 5 ℃ for min -1), and finally the target catalyst was obtained.
The X-ray diffraction pattern of the catalyst obtained by the method described in example 2 is shown in FIG. 1.
The target catalyst obtained in the example 2 is applied to the reaction of preparing benzaldehyde by oxidizing benzyl alcohol with oxygen under the condition of no solvent. 19.2mmol of benzyl alcohol, 50mg of catalyst and then oxygen (2.0 MPa) were added in this order to the autoclave, and the mixture was reacted at 150℃for 5 hours. After the reaction, the catalyst was separated by centrifugation, and the filtrate was diluted with ethanol and analyzed by gas chromatography, and the conversion of benzyl alcohol was calculated to be 31.3% and the selectivity of benzaldehyde was 93.7%.
In addition, the catalyst is centrifugally separated, and the recovered catalyst is washed with ethanol and water successively and dried for use. Under the same reaction conditions, the stability of the catalyst for preparing benzaldehyde by catalytic oxidation of benzyl alcohol is investigated, and the catalyst is circulated. The seventh recovered catalyst in this reaction gave a conversion of 31.0% of benzyl alcohol and a selectivity of 93.2% of benzaldehyde.
Example 3
Five metal precursors, each 1.2mmol),Fe(NO)3·9H2O(0.485g)、Co(OAc)2(0.212g)、Ni(OAc)2·4H2O(0.298g)、Cr(OAc)3(0.275g) and Mn (OAc) 2·4H2 O (0.294 g), were dissolved in 60mL of deionized water, 2.4 mmole Ce (OAc) 3 (0.760 g) was added with continuous stirring, then 2.6 mmole cetyltrimethylammonium bromide (CTAB) was added, the solution was warmed to 60 ℃, stirred for 12h, then 6.0mL of aqueous ammonia (28 wt.%) was added to the solution, and stirring was continued for 12h, the resulting precipitate was isolated by filtration, washed thoroughly with deionized water and ethanol, dried in an oven at 120 ℃ for 4h, the solid catalyst was collected in a crucible, calcined at 900 ℃ for 4h (the warming rate was 5 ℃ for min -1), and finally the target catalyst was obtained.
The target catalyst obtained in the example 3 is applied to the reaction of preparing benzaldehyde by oxidizing benzyl alcohol with oxygen under the condition of no solvent. 19.2mmol of benzyl alcohol, 50mg of catalyst and then oxygen (2.0 MPa) were added in this order to the autoclave, and the mixture was reacted at 150℃for 5 hours. After the reaction, the catalyst was separated by centrifugation, and the filtrate was diluted with ethanol and analyzed by gas chromatography, and the conversion of benzyl alcohol was calculated to be 30.8% and the selectivity of benzaldehyde was 93.7%.
In addition, the catalyst is centrifugally separated, and the recovered catalyst is washed with ethanol and water successively and dried for use. Under the same reaction conditions, the stability of the catalyst for preparing benzaldehyde by catalytic oxidation of benzyl alcohol is investigated, and the catalyst is circulated. The seventh recovered catalyst in this reaction gave a conversion of 30.7% of benzyl alcohol and a selectivity of 93.5% of benzaldehyde.
Example 4
Five metal precursors, each 1.2mmol),Fe(NO)3·9H2O(0.485g)、Co(OAc)2(0.212g)、Ni(OAc)2·4H2O(0.298g)、Cr(OAc)3(0.275g) and Mn (OAc) 2·4H2 O (0.294 g), were dissolved in 60mL of deionized water, 1.8 mmole Ce (OAc) 3 (0.570 g) was added with continuous stirring, then 1.8 mmole cetyltrimethylammonium bromide (CTAB) was added, the solution was warmed to 60 ℃, stirred for 12h, then 6.0mL of aqueous ammonia (28 wt.%) was added to the solution, and stirring was continued for 12h, the resulting precipitate was isolated by filtration, washed thoroughly with deionized water and ethanol, dried in an oven at 120 ℃ for 4h, the solid catalyst was collected in a crucible, calcined at 900 ℃ for 4h (the warming rate was 5 ℃ for min -1), and finally the target catalyst was obtained.
The target catalyst obtained in the example 4 is applied to the reaction of preparing benzaldehyde by oxidizing benzyl alcohol with oxygen under the condition of no solvent. 19.2mmol of benzyl alcohol, 50mg of catalyst and then oxygen (2.0 MPa) were added in this order to the autoclave, and the mixture was reacted at 150℃for 5 hours. After the reaction, the catalyst was separated by centrifugation, and the filtrate was diluted with ethanol and analyzed by gas chromatography, and the conversion of benzyl alcohol was calculated to be 35.7% and the selectivity of benzaldehyde was 96.6%.
In addition, the catalyst is centrifugally separated, and the recovered catalyst is washed with ethanol and water successively and dried for use. Under the same reaction conditions, the stability of the catalyst for preparing benzaldehyde by catalytic oxidation of benzyl alcohol is investigated, and the catalyst is circulated. The seventh recovered catalyst in this reaction gave 35.5% conversion of benzyl alcohol and 96.4% selectivity to benzaldehyde.
Example 5
Five metal precursors, each 1.2mmol),Fe(NO)3·9H2O(0.485g)、Co(OAc)2(0.212g)、Ni(OAc)2·4H2O(0.298g)、Cr(OAc)3(0.275g) and Mn (OAc) 2·4H2 O (0.294 g), were dissolved in 60mL of deionized water, 1.8 mmole Ce (OAc) 3 (0.570 g) was added and stirring continued, then 2.6 mmole cetyltrimethylammonium bromide (CTAB) was added, the solution was warmed to 60 ℃, stirred for 12h, then 10mL of aqueous ammonia (28 wt.%) was added to the solution and stirring continued for 12h, the resulting precipitate was isolated by filtration, washed thoroughly with deionized water and ethanol, dried in an oven at 120 ℃ for 4h. The solid catalyst was collected in a crucible, calcined at 900 ℃ for 4h (the rate of warming was 5 ℃ for min -1), and finally the target catalyst was obtained.
FIG. 2 shows a scanning electron micrograph (a) and a transmission electron micrograph (b) of the catalyst obtained by the method described in example 5.
The target catalyst obtained in the example 5 is applied to the reaction of preparing benzaldehyde by oxidizing benzyl alcohol with oxygen under the condition of no solvent. 19.2mmol of benzyl alcohol, 50mg of catalyst and then oxygen (2.0 MPa) were added in this order to the autoclave, and the mixture was reacted at 150℃for 5 hours. After the reaction, the catalyst was separated by centrifugation, and the filtrate was diluted with ethanol and analyzed by gas chromatography, and the conversion of benzyl alcohol was calculated to be 40.7% and the selectivity of benzaldehyde was 95.6%.
In addition, the catalyst is centrifugally separated, and the recovered catalyst is washed with ethanol and water successively and dried for use. Under the same reaction conditions, the stability of the catalyst for preparing benzaldehyde by catalytic oxidation of benzyl alcohol is investigated, and the catalyst is circulated. The seventh recovered catalyst in this reaction gave a conversion of 40.5% of benzyl alcohol and a selectivity of 95.0% of benzaldehyde.
Example 6
Five metal precursors, each 1.2mmol),Fe(NO)3·9H2O(0.485g)、Co(OAc)2(0.212g)、Ni(OAc)2·4H2O(0.298g)、Cr(OAc)3(0.275g) and Mn (OAc) 2·4H2 O (0.294 g), were dissolved in 60mL of deionized water, 1.8 mmole Ce (OAc) 3 (0.570 g) was added with continuous stirring, then 2.6 mmole cetyltrimethylammonium bromide (CTAB) was added, the solution was warmed to 60 ℃, stirred for 12h, then 6.0mL of aqueous ammonia (28 wt.%) was added to the solution, and stirring was continued for 12h, the resulting precipitate was isolated by filtration, washed thoroughly with deionized water and ethanol, dried in an oven at 120 ℃ for 4h, the solid catalyst was collected in a crucible, calcined at 900 ℃ for 4h (the warming rate was 5 ℃ for min -1), and finally the target catalyst was obtained.
The target catalyst obtained in the example 6 is applied to the reaction of preparing benzaldehyde by oxidizing benzyl alcohol with oxygen under the condition of no solvent. 19.2mmol of benzyl alcohol and 30mg of catalyst were successively added to the autoclave, followed by charging oxygen (2.0 MPa) and reacting at 150℃for 5 hours. After the reaction, the catalyst was separated by centrifugation, and the filtrate was diluted with ethanol and analyzed by gas chromatography, and the conversion of benzyl alcohol was calculated to be 29.0% and the selectivity of benzaldehyde was 83.1%.
In addition, the catalyst is centrifugally separated, and the recovered catalyst is washed with ethanol and water successively and dried for use. Under the same reaction conditions, the stability of the catalyst for preparing benzaldehyde by catalytic oxidation of benzyl alcohol is investigated, and the catalyst is circulated. The seventh recovered catalyst in this reaction gave 28.5% conversion of benzyl alcohol and 82.4% selectivity to benzaldehyde.
Comparative example 1
Five metal precursors, each 1.2mmol),Fe(NO)3·9H2O(0.485g)、Co(OAc)2(0.212g)、Ni(OAc)2·4H2O(0.298g)、Cr(OAc)3(0.275g) and Mn (OAc) 2·4H2 O (0.294 g), were dissolved in 60mL of deionized water, 1.8 mmole Ce (OAc) 3 (0.570 g) was added with continuous stirring, then 2.6 mmole cetyltrimethylammonium bromide (CTAB) was added, the solution was warmed to 60 ℃, stirred for 12h, then 6.0mL of aqueous ammonia (28 wt.%) was added to the solution, and stirring was continued for 12h, the resulting precipitate was isolated by filtration, washed thoroughly with deionized water and ethanol, dried in an oven at 120 ℃ for 4h, the solid catalyst was collected in a crucible, calcined at 600 ℃ for 4h (the warming rate was 5 ℃ min -1), and finally the target catalyst was obtained.
The target catalyst obtained in the practical comparative example 1 is applied to the reaction of preparing benzaldehyde by oxidizing benzyl alcohol with oxygen under the condition of no solvent. 19.2mmol of benzyl alcohol, 50mg of catalyst and then oxygen (2.0 MPa) were added in this order to the autoclave, and the mixture was reacted at 150℃for 5 hours. After the reaction, the catalyst was separated by centrifugation, and the filtrate was diluted with ethanol and analyzed by gas chromatography, and the conversion of benzyl alcohol was calculated to be 17.7% and the selectivity of benzaldehyde was 67.6%.
In addition, the catalyst is centrifugally separated, and the recovered catalyst is washed with ethanol and water successively and dried for use. Under the same reaction conditions, the stability of the catalyst for preparing benzaldehyde by catalytic oxidation of benzyl alcohol is investigated, and the catalyst is circulated. The seventh recovered catalyst in this reaction gave a conversion of 17.2% of benzyl alcohol and a selectivity of 67.0% of benzaldehyde.
Comparative example 2
Five metal precursors, each 1.2mmol),Fe(NO)3·9H2O(0.485g)、Co(OAc)2(0.212g)、Ni(OAc)2·4H2O(0.298g)、Cr(OAc)3(0.275g) and Mn (OAc) 2·4H2 O (0.294 g), were dissolved in 60mL of deionized water, 1.8 mmole Ce (OAc) 3 (0.570 g) was added with continuous stirring, then 2.6 mmole cetyltrimethylammonium bromide (CTAB) was added, the solution was warmed to 60 ℃, stirred for 12h, then 6.0mL of aqueous ammonia (28 wt.%) was added to the solution, and stirring was continued for 12h, the resulting precipitate was isolated by filtration, washed thoroughly with deionized water and ethanol, dried in an oven at 120 ℃ for 4h, the solid catalyst was collected in a crucible, calcined at 900 ℃ for 4h (the warming rate was 5 ℃ for min -1), and finally the target catalyst was obtained.
The target catalyst obtained in the comparative example 2 is applied to the reaction of preparing benzaldehyde by oxidizing benzyl alcohol with oxygen under the condition of no solvent. 19.2mmol of benzyl alcohol and 50mg of catalyst were successively added to the autoclave, followed by charging oxygen (2.0 MPa) and reacting at 100℃for 5 hours. After the reaction, the catalyst was separated by centrifugation, and the filtrate was diluted with ethanol and analyzed by gas chromatography, and the conversion of benzyl alcohol was calculated to be 8.6% and the selectivity of benzaldehyde was 77.6%.
In addition, the catalyst is centrifugally separated, and the recovered catalyst is washed with ethanol and water successively and dried for use. Under the same reaction conditions, the stability of the catalyst for preparing benzaldehyde by catalytic oxidation of benzyl alcohol is investigated, and the catalyst is circulated. The seventh recovered catalyst in this reaction gave a conversion of 8.6% of benzyl alcohol and a selectivity of 77.2% of benzaldehyde.
Comparative example 3
Five metal precursors, each 1.2mmol),Fe(NO)3·9H2O(0.485g)、Co(OAc)2(0.212g)、Ni(OAc)2·4H2O(0.298g)、Cr(OAc)3(0.275g) and Mn (OAc) 2·4H2 O (0.294 g), were dissolved in 60mL of deionized water, 1.8 mmole Ce (OAc) 3 (0.570 g) was added with continuous stirring, then 2.6 mmole cetyltrimethylammonium bromide (CTAB) was added, the solution was warmed to 60 ℃, stirred for 12h, then 6.0mL of aqueous ammonia (28 wt.%) was added to the solution, and stirring was continued for 12h, the resulting precipitate was isolated by filtration, washed thoroughly with deionized water and ethanol, dried in an oven at 120 ℃ for 4h, the solid catalyst was collected in a crucible, calcined at 900 ℃ for 4h (the warming rate was 5 ℃ for min -1), and finally the target catalyst was obtained.
The target catalyst obtained in the comparative example 3 was applied to a reaction for preparing benzaldehyde by oxidizing benzyl alcohol with oxygen under a solvent-free condition. 19.2mmol of benzyl alcohol, 50mg of catalyst and then oxygen (2.0 MPa) were added in this order to the autoclave, and the mixture was reacted at 150℃for 1 hour. After the reaction, the catalyst was separated by centrifugation, and the filtrate was diluted with ethanol and analyzed by gas chromatography, and the conversion of benzyl alcohol was calculated to be 9.5% and the selectivity of benzaldehyde was 88.6%.
In addition, the catalyst is centrifugally separated, and the recovered catalyst is washed with ethanol and water successively and dried for use. Under the same reaction conditions, the stability of the catalyst for preparing benzaldehyde by catalytic oxidation of benzyl alcohol is investigated, and the catalyst is circulated. The seventh recovered catalyst in this reaction gave a benzyl alcohol conversion of 9.2% and a benzaldehyde selectivity of 88.5%.
Further, specific important parameters of the examples and comparative examples of the present invention are shown in the following table 1.
TABLE 1
It can be seen from Table 1 that the conversion and selectivity of comparative examples 1-3 are relatively poor with respect to examples 1-6, whereas the catalysts prepared according to the invention have a conversion of substantially greater than 30% and a selectivity of substantially greater than 90%, especially as best described in examples 4 and 5. Comparing examples 1-6, it is evident from the parameter cases that the Ce content has the greatest effect on the catalyst of the invention, secondly that CTAB is effected by examples 4 and 5, and that ammonia is effected by comparison of examples 5 and 6. Meanwhile, when the catalyst is applied, the effects of the catalysts prepared by different embodiments are obviously different, and the quality, the reaction temperature and the reaction time of the catalyst have different degrees of influence on the subsequent conversion rate and selectivity based on the condition that the quality of benzyl alcohol is unchanged.
The preferred embodiments and comparative examples of the present invention have been described in detail above, and from the foregoing description, the related researchers can make various changes, modifications and combinations without departing from the scope of the technical idea of the present invention. These should also be considered as the disclosure of the present invention, and all fall within the scope of the present invention.
Claims (10)
1. A catalyst for preparing benzaldehyde by oxidizing benzyl alcohol with oxygen under a solvent-free condition is characterized in that the catalyst is cerium doped high-entropy oxide, wherein the high-entropy oxide is (FeCoNiCrMn) 3O4.
2. The preparation method of the catalyst for preparing benzaldehyde by oxidizing benzyl alcohol with oxygen under the condition of no solvent is characterized by comprising the following steps:
(1) Fe(NO)3·9H2O、Co(OAc)2、Ni(OAc)2·4H2O、Cr(OAc)3、Mn(OAc)2·4H2O is dissolved in deionized water, fully stirred, a certain amount of Ce (OAc) 3 and surfactant are added, and stirred for 12 hours at 60 ℃;
(2) Adding ammonia water, continuously stirring for 12 hours, collecting a solid product, and drying in an oven;
(3) Placing the solid in a muffle furnace, and calcining for a certain time at a certain temperature to obtain the catalyst.
3. The method for preparing a catalyst for preparing benzaldehyde by oxidizing benzyl alcohol with oxygen under solvent-free condition as claimed in claim 2, wherein said surfactant is cetyltrimethylammonium bromide; the mass fraction of the ammonia water is 28%.
4. The method for preparing a catalyst for preparing benzaldehyde by oxidizing benzyl alcohol with oxygen under solvent-free condition as claimed in claim 2, wherein in step (1), ce: fe: co: ni: cr: the mole ratio of Mn metal precursor is (0.2-5): 1:1:1:1: the molar ratio of the Ce metal precursor to the surfactant is 1: (0.5-5).
5. The method for preparing a catalyst for preparing benzaldehyde by oxidizing benzyl alcohol with oxygen under solvent-free condition as claimed in claim 4, wherein in the step (2), the ratio of the amount of Ce precursor to ammonia water is 1mmol: (1-20) mL.
6. The method for preparing a catalyst for preparing benzaldehyde by oxidizing benzyl alcohol with oxygen under solvent-free condition as claimed in claim 4, wherein in the step (3), the calcination temperature is 600-1000 ℃ and the calcination time is 2-8 h.
7. The catalyst obtained by the preparation method according to any one of claims 2 to 6 is used for preparing benzaldehyde by oxidizing benzyl alcohol with oxygen under a solvent-free condition.
8. The use of the catalyst according to claim 7, comprising the following: and (3) placing benzyl alcohol in a high-pressure reaction kettle with a quartz lining, filling oxygen, fully stirring, adding the catalyst, reacting for a certain time at a specific temperature, centrifuging or filtering to separate a solid catalyst, and quantitatively analyzing the reaction liquid by using a gas chromatography external standard.
9. The use of the catalyst according to claim 8, wherein the reaction temperature is 80-200 ℃ and the reaction time is 2-10 h.
10. The use of the catalyst according to claim 8, wherein the ratio of the catalyst mass to the benzyl alcohol molar amount is (0.5-10) mg:1mmol.
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