CN116102409A - Method for synthesizing 2-methoxy-4-methylphenol by using vanillin liquid phase - Google Patents
Method for synthesizing 2-methoxy-4-methylphenol by using vanillin liquid phase Download PDFInfo
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- CN116102409A CN116102409A CN202310057431.0A CN202310057431A CN116102409A CN 116102409 A CN116102409 A CN 116102409A CN 202310057431 A CN202310057431 A CN 202310057431A CN 116102409 A CN116102409 A CN 116102409A
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- methoxy
- methylphenol
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- vanillin
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- PETRWTHZSKVLRE-UHFFFAOYSA-N 2-Methoxy-4-methylphenol Chemical compound COC1=CC(C)=CC=C1O PETRWTHZSKVLRE-UHFFFAOYSA-N 0.000 title claims abstract description 96
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 title claims abstract description 37
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 235000012141 vanillin Nutrition 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 11
- 239000007791 liquid phase Substances 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 235000019253 formic acid Nutrition 0.000 claims abstract description 15
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 20
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 15
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 12
- 239000011780 sodium chloride Substances 0.000 claims description 10
- 239000001103 potassium chloride Substances 0.000 claims description 9
- 235000011164 potassium chloride Nutrition 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910002668 Pd-Cu Inorganic materials 0.000 claims description 2
- 229910021069 Pd—Co Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 2
- 238000003801 milling Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000001257 hydrogen Substances 0.000 abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 10
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 150000004678 hydrides Chemical class 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract 1
- ZENOXNGFMSCLLL-UHFFFAOYSA-N vanillyl alcohol Chemical compound COC1=CC(CO)=CC=C1O ZENOXNGFMSCLLL-UHFFFAOYSA-N 0.000 description 26
- 239000000047 product Substances 0.000 description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000006227 byproduct Substances 0.000 description 12
- 238000005984 hydrogenation reaction Methods 0.000 description 9
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- 239000012075 bio-oil Substances 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for synthesizing 2-methoxy-4-methylphenol by using vanillin liquid phase, and relates to the technical field of fine chemical engineering. The invention takes vanillin as raw material and Ti as raw material 3 C 2 The Pd-M catalyst liquid phase catalyzes the methanoic acid to produce hydrogen for reduction to prepare 2-methoxy-4 methylphenol, the selectivity of the target product is high, the reaction temperature can be obviously reduced by in-situ hydrogen release of the hydride, and the catalyst still maintains good catalytic activity after repeated recycling. The invention utilizes formic acid to release hydrogen in situ to catalyze vanillin to selectively hydrogenate 2-methoxy-4 methylphenol under mild condition, which is of great significance for mass production of 2-methoxy-4 methylphenol.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, in particular to a method for synthesizing 2-methoxy-4-methylphenol by using vanillin liquid phase.
Background
With the increasing exhaustion of fossil resources and the increasing environmental pollution caused by the large-scale use of fossil resources, the development and utilization of renewable energy sources have received a great deal of attention. The bio-oil produced by the rapid pyrolysis of biomass is a green renewable liquid fuel and is expected to replace the existing fossil fuel. However, the high oxygen content of the bio-oil limits the large-scale application of the bio-oil, and the development of the biomass hydrodeoxygenation technology has important significance on the physique and the efficient utilization of biomass.
Vanillin is an oxygen-containing compound obtained by pyrolysis of biomass lignin, and a hydrogenation product 2-methoxy-4 methylphenol is a biofuel with a very good application prospect, and is also a chemical raw material with important application in essence synthesis and organic synthesis reactions. The method for synthesizing 2-methoxy-4-methylphenol by utilizing vanillin hydrodeoxygenation is an important method for producing 2-methoxy-4-methylphenol, and the existing catalytic technology generally requires high temperature and high pressure, hydrogen to participate in and acid and alkali to be added, so that the development of the 2-methoxy-4-methylphenol production technology is severely limited. Therefore, the development of a mild, green and efficient process for synthesizing 2-methoxy-4-methylphenol by hydrodeoxygenation of vanillin is urgent.
Disclosure of Invention
The invention aims to provide a method for synthesizing 2-methoxy-4-methylphenol by using vanillin liquid phase, which solves the problems in the prior art and realizes a new idea of synthesizing 2-methoxy-4-methylphenol.
In order to achieve the above object, the present invention provides the following solutions:
the invention provides a method for synthesizing 2-methoxy-4-methylphenol by using vanillin liquid phase, which comprises the following steps:
under protective atmosphere, ti 3 C 2 Mixing the Pd-M catalyst with vanillin and formic acid, then reacting under the irradiation of visible light, and removing the catalyst after the reaction is finished to obtain 2-methoxy-4 methylphenol;
the Ti is 3 C 2 The catalyst Pd-M is Ti 3 C 2 /Pd-Co、Ti 3 C 2 Pd-Ni or Ti 3 C 2 /Pd-Cu。
Further, the reaction temperature is 20-60 ℃.
Further, the Ti is 3 C 2 The mass ratio of the Pd-M catalyst to the vanillin and the formic acid is 1 (5-8) to 8-10.
Catalyst Ti 3 C 2 in/Pd-M, ti 3 C 2 Derived from Ti 3 AlC 2 Pd is derived from palladium chloride and M is derived from CoCl 2 、NiCl 2 、CuCl 2 Is one of (a);
further, the Ti is 3 C 2 The preparation method of the Pd-M catalyst comprises the following steps:
ti is mixed with 3 AlC 2 Palladium chloride and MCl 2 Mixing and grinding, roasting the obtained mixture, washing with water and drying to obtain Ti 3 C 2 Pd-M catalyst; the MCl 2 M in (C) is Co, ni or Cu.
Further, the Ti is 3 AlC 2 Palladium chloride and MCl 2 The mass ratio of (2) is 1: (0.1-0.3): (1-3).
Further, the roasting temperature is 650-900 ℃ and the roasting time is 8.0-16.0 h.
Further, sodium chloride and potassium chloride are added in the grinding process; the Ti is 3 AlC 2 The mass ratio of the sodium chloride to the potassium chloride is 1: (1-2): (3-5).
The invention discloses the following technical effects:
the invention uses Ti 3 AlC 2 Palladium chloride and MCl 2 The precursor is prepared by in-situ substitution of Al through roasting, and the regulation and control of the electronic structure of the catalyst are realized by regulating the proportion of Pd and M (one of Co, ni and Cu), so that the hydrogenation activity of the catalyst is obviously improved.
The invention adopts Ti 3 C 2 The Pd-M is used as a catalyst, formic acid in-situ hydrogen release is used as a hydrogen source, the synthesis of the high-selectivity 2-methoxy-4-methylphenol under the actions of mild conditions and visible light can be realized, the conversion rate is 100%, the selectivity of the target product 2-methoxy-4-methylphenol can reach more than 99%, and the byproductThe product vanillyl alcohol is below 1%, which is far superior to high pressure hydrogenation, especially by in situ hydrogen release of hydride, the reaction temperature can be obviously reduced, and the catalyst can still maintain good catalytic activity after being recycled for 100 times. The development of the process for synthesizing 2-methoxy-4-methylphenol by in-situ hydrogen release and high-efficiency catalytic vanillin selective hydrogenation under mild conditions has important significance for mass production of 2-methoxy-4-methylphenol.
The invention takes vanillin as raw material and Ti as raw material 3 C 2 The Pd-M catalyst liquid phase catalytic formic acid hydrogen production reduction to prepare 2-methoxy-4 methylphenol is a novel method for preparing 2-methoxy-4 methylphenol with high selectivity.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
Example 1
(1) Preparation of the catalyst
1g of Ti is weighed 3 AlC 2 Added to 0.1g of palladium chloride and 1g of NiCl 2 Is placed in a mortar for full grinding. Further weighing 1g of sodium chloride and 3g of potassium chloride, adding into the mixture, fully grinding, transferring into a quartz boat, placing into a tube furnace, roasting at 650 ℃ for 16.0h, washing with water, and drying to obtain Ti 3 C 2 /Pd 0.1 -Ni catalyst, stored in a closed state.
(2) Taking the prepared Ti 3 C 2 /Pd 0.1 Placing 0.1g of Ni catalyst in a photochemical reactor, introducing nitrogen for replacement, then injecting 0.5g of vanillin and 0.8g of formic acid into the photochemical reactor, stirring, heating to 20 ℃ for reaction, starting visible light irradiation, and removing the catalyst after the reaction is finished to obtain the target product 2-methoxy-4 methylphenol. The product after reaction was analyzed by gas chromatography-mass spectrometry, the conversion rate of vanillin was 100%, the selectivity of 2-methoxy-4 methylphenol was 99.2%, and the selectivity of the by-product vanillyl alcohol was 0.8%. After the catalyst is recycled for 100 times, the conversion rate of vanillin is 100%, the selectivity of the product 2-methoxy-4 methylphenol is 99.1%, the selectivity of the byproduct vanillyl alcohol is 0.9%, and the catalyst has good catalytic stability.
Example 2
(1) Preparation of the catalyst
1g of Ti is weighed 3 AlC 2 Added to 0.3g of palladium chloride and 3g of NiCl 2 Is placed in a mortar for full grinding. Further weighing 2g of sodium chloride and 5g of sodium chlorideAdding potassium into the above mixture, grinding, transferring into quartz boat, placing into tube furnace, roasting at 900deg.C for 8.0 hr, washing with water, and drying to obtain Ti 3 C 2 /Pd 0.3 -Ni 3 And (3) the catalyst is stored in a closed manner.
(2) Hydrogenation for preparing 2-methoxy-4-methylphenol
Taking the prepared Ti 3 C 2 /Pd 0.3 -Ni 3 Placing 0.1g of catalyst in a photochemical reactor, introducing nitrogen for replacement, then injecting 0.8g of vanillin and 1.0g of formic acid into the photochemical reactor, stirring, heating to 60 ℃ for reaction, starting visible light irradiation, and removing the catalyst after the reaction is finished to obtain the target product 2-methoxy-4 methylphenol. The product after reaction was analyzed by gas chromatography-mass spectrometry, the conversion rate of vanillin was 100%, the selectivity of 2-methoxy-4 methylphenol was 99.5%, and the selectivity of the by-product vanillyl alcohol was 0.5%. After the catalyst is recycled for 100 times, the conversion rate of vanillin is 100%, the selectivity of the product 2-methoxy-4 methylphenol is 99.4%, the selectivity of the byproduct vanillyl alcohol is 0.6%, and the catalyst has good catalytic stability.
Example 3
(1) Preparation of the catalyst
1g of Ti is weighed 3 AlC 2 Added to 0.3g of palladium chloride and 1g of CoCl 2 Is placed in a mortar for full grinding. Further weighing 1.5g of sodium chloride and 4g of potassium chloride, adding into the mixture, fully grinding, transferring into a quartz boat, placing into a tube furnace, roasting at 900 ℃ for 16.0h, washing with water, and drying to obtain Ti 3 C 2 /Pd 0.3 -Co catalyst, stored in a closed state.
(2) Hydrogenation for preparing 2-methoxy-4-methylphenol
Taking the prepared Ti 3 C 2 /Pd 0.3 Placing 0.1g of Co catalyst into a photochemical reactor, introducing nitrogen for replacement, then injecting 0.5g of vanillin and 0.8g of formic acid into the photochemical reactor, stirring, heating to 50 ℃ for reaction, starting visible light irradiation, and removing the catalyst after the reaction is finished to obtain the target product 2-Methoxy-4 methylphenol. The product after reaction was analyzed by gas chromatography-mass spectrometry, the conversion rate of vanillin was 100%, the selectivity of 2-methoxy-4 methylphenol was 99.4%, and the selectivity of the by-product vanillyl alcohol was 0.6%. After the catalyst is recycled for 100 times, the conversion rate of vanillin is 100%, the selectivity of the product 2-methoxy-4 methylphenol is 99.2%, the selectivity of the byproduct vanillyl alcohol is 0.8%, and the catalyst keeps good catalytic stability.
Example 4
(1) Preparation of the catalyst
1g of Ti is weighed 3 AlC 2 Added to 0.1g of palladium chloride and 2g of CoCl 2 Is placed in a mortar for full grinding. Further weighing 1.5g of sodium chloride and 5g of potassium chloride, adding into the mixture, fully grinding, transferring into a quartz boat, placing into a tube furnace, roasting at 800 ℃ for 12.0h, washing with water, and drying to obtain Ti 3 C 2 /Pd 0.1 -Co 2 And (3) the catalyst is stored in a closed manner.
(2) Hydrogenation for preparing 2-methoxy-4-methylphenol
Taking the prepared Ti 3 C 2 /Pd 0.1 -Co 2 Placing 0.1g of catalyst in a photochemical reactor, introducing nitrogen for replacement, then injecting 0.6g of vanillin and 0.9g of formic acid into the photochemical reactor, stirring, heating to 40 ℃ for reaction, starting visible light irradiation, and removing the catalyst after the reaction is finished to obtain the target product 2-methoxy-4 methylphenol. The product after reaction was analyzed by gas chromatography-mass spectrometry, the conversion rate of vanillin was 100%, the selectivity of 2-methoxy-4 methylphenol was 99.3%, and the selectivity of the by-product vanillyl alcohol was 0.7%. After the catalyst is recycled for 100 times, the conversion rate of vanillin is 100%, the selectivity of the product 2-methoxy-4 methylphenol is 99.2%, the selectivity of the byproduct vanillyl alcohol is 0.8%, and the catalyst keeps good catalytic stability.
Example 5
(1) Preparation of the catalyst
1g of Ti is weighed 3 AlC 2 Added to 0.2g of palladium chloride and 1g of CuCl 2 Is placed in a mortar for full grinding.Further weighing 2g of sodium chloride and 3g of potassium chloride, adding into the mixture, fully grinding, transferring into a quartz boat, placing into a tube furnace, roasting at 700 ℃ for 16.0h, washing with water, and drying to obtain Ti 3 C 2 /Pd 0.2 -Cu catalyst, stored in a closed state.
(2) Hydrogenation for preparing 2-methoxy-4-methylphenol
Taking the prepared Ti 3 C 2 /Pd 0.2 Placing 0.1g of Cu catalyst in a photochemical reactor, introducing nitrogen for replacement, then injecting 0.7g of vanillin and 1.0g of formic acid into the photochemical reactor, stirring, heating to 30 ℃ for reaction, starting visible light irradiation, and removing the catalyst after the reaction is finished to obtain the target product 2-methoxy-4 methylphenol. The product after reaction was analyzed by gas chromatography-mass spectrometry, the conversion rate of vanillin was 100%, the selectivity of 2-methoxy-4 methylphenol was 99.1%, and the selectivity of the by-product vanillyl alcohol was 0.9%. After the catalyst is recycled for 100 times, the conversion rate of vanillin is 100%, the selectivity of the product 2-methoxy-4 methylphenol is 99.0%, the selectivity of the byproduct vanillyl alcohol is 1.0%, and the catalyst keeps good catalytic stability.
Example 6
(1) Preparation of the catalyst
1g of Ti is weighed 3 AlC 2 Added to 0.2g of palladium chloride and 3g of CuCl 2 Is placed in a mortar for full grinding. Further weighing 2g of sodium chloride and 5g of potassium chloride, adding into the mixture, fully grinding, transferring into a quartz boat, placing into a tube furnace, roasting at 900 ℃ for 16.0h, washing with water, and drying to obtain Ti 3 C 2 /Pd 0.2 -Cu 3 And (3) the catalyst is stored in a closed manner.
(2) Hydrogenation for preparing 2-methoxy-4-methylphenol
Taking the prepared Ti 3 C 2 /Pd 0.2 -Cu 3 Placing 0.1g of catalyst in a photochemical reactor, introducing nitrogen for replacement, then injecting 0.5g of vanillin and 1.0g of formic acid into the photochemical reactor, stirring, heating to 60 ℃ for reaction, starting visible light irradiation, and removing after the reaction is finishedRemoving the catalyst to obtain the target product 2-methoxy-4 methylphenol. The product after reaction was analyzed by gas chromatography-mass spectrometry, the conversion rate of vanillin was 100%, the selectivity of 2-methoxy-4 methylphenol was 99.7%, and the selectivity of the by-product vanillyl alcohol was 0.3%. After the catalyst is recycled for 100 times, the conversion rate of vanillin is 100%, the selectivity of the product 2-methoxy-4 methylphenol is 99.6%, the selectivity of the byproduct vanillyl alcohol is 0.4%, and the catalyst keeps good catalytic stability.
The invention takes vanillin as raw material and Ti as raw material 3 C 2 The Pd-M catalyst liquid phase catalyzes the methanoic acid to produce hydrogen for reduction to prepare high-selectivity 2-methoxy-4 methylphenol, the reaction condition is mild, and the catalyst has good catalytic activity, selectivity and stability.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (7)
1. A method for synthesizing 2-methoxy-4-methylphenol by using vanillin liquid phase, which is characterized by comprising the following steps:
under protective atmosphere, ti 3 C 2 Mixing the Pd-M catalyst with vanillin and formic acid, then reacting under the irradiation of visible light, and removing the catalyst after the reaction is finished to obtain 2-methoxy-4 methylphenol;
the Ti is 3 C 2 The catalyst Pd-M is Ti 3 C 2 /Pd-Co、Ti 3 C 2 Pd-Ni or Ti 3 C 2 /Pd-Cu。
2. The method according to claim 1, wherein the reaction temperature is 20 to 60 ℃.
3. The method according to claim 1, wherein the Ti 3 C 2 /Pd-MThe mass ratio of the catalyst to vanillin to formic acid is 1 (5-8) to 8-10.
4. The method according to claim 1, wherein the Ti 3 C 2 The preparation method of the Pd-M catalyst comprises the following steps:
ti is mixed with 3 AlC 2 Palladium chloride and MCl 2 Mixing and grinding, roasting the obtained mixture, washing with water and drying to obtain Ti 3 C 2 Pd-M catalyst;
the MCl 2 M in (C) is Co, ni or Cu.
5. The method according to claim 4, wherein the Ti is 3 AlC 2 Palladium chloride and MCl 2 The mass ratio of (2) is 1: (0.1-0.3): (1-3).
6. The method according to claim 4, wherein the firing temperature is 650 to 900 ℃ and the firing time is 8.0 to 16.0 hours.
7. The method according to claim 4, wherein sodium chloride and potassium chloride are also added during the milling process; the Ti is 3 AlC 2 The mass ratio of the sodium chloride to the potassium chloride is 1: (1-2): (3-5).
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310057431.0A CN116102409B (en) | 2023-01-17 | 2023-01-17 | Method for synthesizing 2-methoxy-4-methylphenol by using vanillin liquid phase |
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| CN202310057431.0A CN116102409B (en) | 2023-01-17 | 2023-01-17 | Method for synthesizing 2-methoxy-4-methylphenol by using vanillin liquid phase |
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| CN107537540A (en) * | 2017-08-28 | 2018-01-05 | 浙江工业大学 | A kind of MXene (Ti3C2) loaded palladium catalyst and its preparation method and application |
| CN114573429A (en) * | 2022-02-28 | 2022-06-03 | 陕西科技大学 | Preparation method of 2-methoxy-4 methylphenol based on selective hydrodeoxygenation of vanillin |
| CN114656337A (en) * | 2022-04-22 | 2022-06-24 | 陕西科技大学 | Method for preparing 2-methoxy-4-methylphenol from biomass-based vanillin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107537540A (en) * | 2017-08-28 | 2018-01-05 | 浙江工业大学 | A kind of MXene (Ti3C2) loaded palladium catalyst and its preparation method and application |
| CN114573429A (en) * | 2022-02-28 | 2022-06-03 | 陕西科技大学 | Preparation method of 2-methoxy-4 methylphenol based on selective hydrodeoxygenation of vanillin |
| CN114656337A (en) * | 2022-04-22 | 2022-06-24 | 陕西科技大学 | Method for preparing 2-methoxy-4-methylphenol from biomass-based vanillin |
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| CN118420442A (en) * | 2024-07-05 | 2024-08-02 | 天津市职业大学 | Method for preparing vanillin by reducing vanillin with silicon powder |
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