CN115160111A - Green catalysis method for vanillin hydrodeoxygenation reaction - Google Patents

Green catalysis method for vanillin hydrodeoxygenation reaction Download PDF

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CN115160111A
CN115160111A CN202210897113.0A CN202210897113A CN115160111A CN 115160111 A CN115160111 A CN 115160111A CN 202210897113 A CN202210897113 A CN 202210897113A CN 115160111 A CN115160111 A CN 115160111A
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袁冰
张泽晓
解从霞
于凤丽
于世涛
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Qingdao University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
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    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
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    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0215—Sulfur-containing compounds
    • B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
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Abstract

The invention relates to a green catalysis method for preparing 2-methoxy-4-methylphenol through vanillin hydrogenation deoxidation reaction, in particular to a method for preparing 2-methoxy-4-methylphenol through vanillin hydrogenation deoxidation reaction catalyzed by Pd nano particles which are stably reduced in a water phase by sodium lignosulfonate, and belongs to the technical field of biomass catalytic conversion. The invention utilizes the sodium lignin sulfonate which is a derivatization product of black liquor of the paper industry as a reducing agent and a stabilizing agent, reduces and stabilizes metal Pd nano particles in a water phase under the condition of no other auxiliary reagent, and directly uses the obtained water phase catalytic system for preparing 2-methoxy-4-methylphenol by vanillin hydrodeoxygenation. The metal Pd nano particle water phase catalysis system can be self-separated from the organic phase product after reaction, and the catalyst has good recycling performance. The method has the advantages of reaction effectiveness and separation simplicity, and the catalytic system and the catalytic process are environment-friendly, so that the method is a green catalytic process for the vanillin hydrodeoxygenation reaction.

Description

Green catalysis method for vanillin hydrodeoxygenation reaction
Technical Field
The invention relates to a green catalysis method for preparing 2-methoxy-4-methylphenol through vanillin hydrogenation deoxidation reaction, in particular to a method for preparing 2-methoxy-4-methylphenol through vanillin hydrogenation deoxidation reaction catalyzed by Pd nano particles which are stably reduced in a water phase by sodium lignosulfonate, and belongs to the field of biomass catalytic conversion.
Background
Vanillin (3-methoxy-4-hydroxybenzaldehyde) is available in large quantities as a natural phenolic compound from industrial lignin, and has been considered as one of the typical lignin model compounds and the most potential renewable lignin-derived platform compounds. Wherein, the 2-methoxy-4-methylphenol (MMP) product obtained by the hydrodeoxygenation reaction of vanillin is an important intermediate of medicine and pesticide and is a biomass fuel with future potential. Therefore, the research on the vanillin Hydrodeoxygenation (HDO) reaction has important significance for increasing the value of the lignin biomass resources.
At present, most researches on the vanillin hydrodeoxygenation reaction use commercial catalysts such as palladium/carbon and ruthenium/carbon, or metal nanoparticle catalysts loaded on solid phase carriers such as molecular sieves, phenolic resins and organic frameworks. The preparation of the immobilized metal nanoparticles generally needs to adopt reagents such as sodium borohydride, hydrazine, dimethylformamide, polyhydric alcohol and the like to reduce in a certain dispersion system or to reduce at high temperature in the atmosphere of hydrogen and the like, the preparation process is complex, the energy consumption is large, and a non-environment-friendly reducing agent is used. On the other hand, if it is desired to obtain metal nanoparticles in a solution independently of a solid carrier, various types of Capping agents (Capping agents) or Encapsulating agents (Encapsulating agents) are involved, thereby effectively preventing the formed metal particles from aggregating to large-sized particles. Various polymers, dendritic macromolecules, surfactants, organic ligands, polyoxometallates and the like which are needed to be used in the process often cause serious pollution to water bodies. Therefore, if the cheap natural renewable resources are used as raw materials or media, the metal catalyst is prepared under the environment-friendly condition and efficiently catalyzes the vanillin HDO reaction, and the catalyst can be simply recycled and reused, a green new method is expected to be provided for the utilization of vanillin resources and the preparation of MMP products.
In recent years, the water-soluble derivative Sodium Lignin Sulfonate (SLS) of lignin can play a role in reducing and stably dispersing metal in aqueous solution due to a macromolecular stable structure and various reductive functional groups, and stable metal nanoparticles can be prepared without adding any other chemical reagent, so that the possibility is provided for the construction of a novel environment-friendly catalytic system while industrial waste is recycled. However, the research on the preparation of metal nanoparticles by using sodium lignosulfonate for reduction and stabilization currently only remains on a simple test of reduction and stabilization behavior and possibly catalytic performance, and the research on the actual chemical reaction of the metal nanoparticles, such as the efficient conversion of biomass through catalytic hydrogenation and the like, is rarely reported. So far, no domestic and foreign literature reports exist on the method for preparing MMP by catalyzing vanillin hydrodeoxygenation through a lignin-reduced and stable transition metal nanoparticle aqueous phase system.
Disclosure of Invention
The method utilizes the synergistic effect of different functional groups in the sodium lignosulfonate structure, reduces the sodium chloropalladate in the water phase without any additional reducing agent, stabilizer and organic solvent, and simultaneously disperses stably generated palladium nano particles to obtain a water phase catalytic system, and catalyzes the hydrodeoxygenation reaction of vanillin in an intermittent reactor to efficiently prepare MMP.
The invention aims to solve the problems that the preparation and stabilization processes of metal nanoparticle catalytic active components and the catalytic reaction process of the vanillin catalytic hydrodeoxygenation process in the prior art are difficult to avoid the use of chemical reducing agents, surfactants, organic solvents and the like, so that an environment-friendly new method for efficiently preparing MMP by utilizing the structural characteristics of sodium lignosulfonate is provided, stabilizing metal palladium nanoparticles in an aqueous phase by one-pot reduction, and directly adopting the aqueous dispersion system to catalyze vanillin hydrodeoxygenation reaction under mild conditions.
The technical scheme of the invention is as follows:
preparing a solution according to the proportion of 0.6g sodium lignosulfonate and 60mL water per millimole of sodium chloropalladate, and reacting for 3h at 40 ℃ under the magnetic stirring of 400rpm to obtain a stable black-brown opaque aqueous phase metal Pd nanoparticle catalytic system, which is named as SLSRePd-3h.
Adding a certain amount of vanillin into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining according to the quantitative ratio n of vanillin to a catalyst active center Pd substance (Vanillin) /n (Pd) =10-300 the SLSREPD-3H aqueous phase catalyst prepared above, and add solvent water to 6mL water per millimole vanillin, seal the kettle and replace air with hydrogen, at 0.5-1.5MPa initial H 2 Reacting for 1-2.5h at 50-80 ℃ under the magnetic stirring of 400rpm under the pressure, standing and layering the mixture after the reaction is finished, and supplementing fresh catalyst with the same concentration to the original catalyst amount for direct reuse after the upper-layer aqueous phase catalyst is separated and recycled.
Compared with the prior art, the method for preparing MMP by catalyzing vanillin hydrodeoxygenation through sodium lignosulfonate aqueous phase reduction and stable metal palladium nano particles has the following characteristics:
(1) The invention provides a method for preparing a metal nanoparticle catalyst in a water phase by using a waste biomass derivatization product sodium lignin sulfonate as a reducing agent and a stabilizing agent of a metal active component at the same time and directly catalyzing vanillin hydrodeoxygenation reaction, which is simple, convenient and easy to implement, clean and cheap;
(2) The method provided by the invention does not need any organic solvent or other chemical reagents in the preparation stage of the catalyst and the catalytic hydrodeoxygenation reaction stage, and has mild reaction conditions and environmental friendliness;
(3) The catalytic vanillin hydrodeoxygenation method provided by the invention is quasi-homogeneous catalysis, has very high catalytic activity and MMP product selectivity, the only byproduct is a small amount of vanillyl alcohol (HMP), and a water-phase catalyst system of the catalytic vanillin hydrodeoxygenation method can be self-separated from a product phase and can be reused by directly separating liquid, so that the catalytic performance is stable.
Detailed description of the preferred embodiment
The process of the present invention is further illustrated, but not limited, by the following specific examples.
Example 1 preparation of Metal Pd nanoparticle catalyst SLSRePd-3h stabilized by sodium Lignosulfonate reduction
Adding 60mg of sodium lignosulfonate which is dried in vacuum at 50 ℃ for 12 hours, 0.1mmol of sodium chloropalladate and 6mL of ultrapure water into a 25mL single-neck flask, heating the obtained solution to 40 ℃, and carrying out magnetic stirring reaction at 400rpm for 3 hours to obtain an aqueous phase metal Pd nanoparticle catalyst SLSRePd-3 hours.
FIG. 1 shows the gradual process of reduction and stabilization of sodium chloropalladate by sodium lignosulfonate solution; figure 2 shows that after 3 hours of reduction and stabilization by sodium lignosulfonate, zero-valent palladium is generated. Figure 3 shows the stable dispersion effect of sodium lignosulfonate on the generated Pd metal nanoparticles.
[ example 2 ]
6mL of SLSREPD-3H aqueous phase catalyst prepared in example 1 and 1mmol (152 mg) of vanillin were charged into a stainless steel autoclave with a Teflon liner, the autoclave was sealed, and after displacing the air with hydrogen, the initial H at 1MPa 2 The reaction was carried out under pressure at 400rpm with magnetic stirring at 50 ℃ for 1 hour. After the reaction, the reaction mixture was extracted with ethyl acetate and quantitatively analyzed by gas chromatography, and the results are shown in Table 1.
[ example 3 ]
A stainless steel autoclave equipped with a polytetrafluoroethylene inner liner was charged with 0.6mL of SLSREPD-3H aqueous phase catalyst prepared in example 1 and 1mmol (152 mg) of vanillin, 5.4mL of ultrapure water was added, the autoclave was sealed, and after replacing the air with hydrogen, the initial H at 1MPa 2 The reaction was carried out at 50 ℃ for 1 hour under pressure and magnetic stirring at 400 rpm. After the reaction was completed, the reaction mixture was extracted with ethyl acetate and quantitatively analyzed by gas chromatography, and the results are shown in Table 1.
[ example 4 ]
0.2mL of SLSREPD-3H aqueous phase catalyst prepared in example 1 and 1mmol (152 mg) of vanillin were charged into a stainless steel autoclave equipped with a polytetrafluoroethylene inner liner, 5.8mL of ultrapure water was added, the autoclave was sealed, and after replacing the air with hydrogen, the initial H at 1MPa 2 The reaction was carried out under pressure at 400rpm with magnetic stirring at 50 ℃ for 1 hour. After the reaction, the reaction mixture was extracted with ethyl acetate and quantitatively analyzed by gas chromatography, and the results are shown in Table 1.
[ example 5 ]
0.2mL of SLSREPD-3H aqueous phase catalyst prepared in example 1 and 1mmol (152 mg) of vanillin were charged into a stainless steel autoclave equipped with a polytetrafluoroethylene inner liner, 5.8mL of ultrapure water was added, the autoclave was sealed, and after replacing the air with hydrogen, the initial H at 1MPa 2 The reaction was carried out at 50 ℃ for 2 hours under pressure and magnetic stirring at 400 rpm. After the reaction, the reaction mixture was extracted with ethyl acetate and quantitatively analyzed by gas chromatography, and the results are shown in Table 1.
[ example 6 ]
0.2mL of SLSREPD-3H aqueous phase catalyst prepared in example 1 and 1mmol (152 mg) of vanillin were charged into a stainless steel autoclave equipped with a polytetrafluoroethylene inner liner, 5.8mL of ultrapure water was added, the autoclave was sealed, and after replacing the air with hydrogen, the initial H at 1MPa 2 The reaction was carried out under pressure at 400rpm with magnetic stirring at 50 ℃ for 2.5h. After the reaction, the reaction mixture was extracted with ethyl acetate and quantitatively analyzed by gas chromatography, and the results are shown in Table 1.
[ example 7 ]
0.2mL of SLSREPD-3H aqueous phase catalyst prepared in example 1 and 1mmol (152 mg) of vanillin were charged into a stainless steel autoclave equipped with a polytetrafluoroethylene inner liner, 5.8mL of ultrapure water was added, the autoclave was sealed, and after replacing the air with hydrogen, the initial H at 1MPa 2 The reaction was carried out at 70 ℃ for 2 hours under pressure and magnetic stirring at 400 rpm. After the reaction, the reaction mixture was extracted with ethyl acetate and quantitatively analyzed by gas chromatography, and the results are shown in Table 1.
[ example 8 ]
To a stainless steel autoclave with a Teflon liner was added 0.2mL of SLSREPD-3 prepared in example 1 H aqueous phase catalyst and 1mmol (152 mg) of vanillin, and 5.8mL of ultrapure water was added, the vessel was sealed, and after replacing the air with hydrogen, at an initial H of 1MPa 2 The reaction was carried out at 80 ℃ for 2 hours under pressure and magnetic stirring at 400 rpm. After the reaction, the reaction mixture was extracted with ethyl acetate and quantitatively analyzed by gas chromatography, and the results are shown in Table 1.
[ example 9 ]
0.2mL of SLSREPD-3H aqueous phase catalyst prepared in example 1 and 1mmol (152 mg) of vanillin were added to a stainless steel autoclave equipped with a Teflon liner, 5.8mL of ultrapure water was added, the autoclave was sealed, and after replacing the air with hydrogen, the initial H at 0.5MPa 2 The reaction was carried out at 70 ℃ for 2 hours under pressure and magnetic stirring at 400 rpm. After the reaction, the reaction mixture was extracted with ethyl acetate and quantitatively analyzed by gas chromatography, and the results are shown in Table 1.
[ example 10 ]
0.2mL of SLSREPD-3H aqueous phase catalyst prepared in example 1 and 1mmol (152 mg) of vanillin were added to a stainless steel autoclave equipped with a Teflon liner, 5.8mL of ultrapure water was added, the autoclave was sealed, and after replacing the air with hydrogen, the initial H at 1.5MPa 2 The reaction was carried out at 70 ℃ for 2 hours under pressure and magnetic stirring at 400 rpm. After the reaction, the reaction mixture was extracted with ethyl acetate and quantitatively analyzed by gas chromatography, and the results are shown in Table 1.
TABLE 1 sodium lignosulfonate reduction-stable metal Pd nanoparticle SLSRePd-3h catalytic vanillin hydrodeoxygenation reaction performance
Figure BDA0003769495220000041
[ examples 11 to 21 ]
After the reaction was completed under the conditions of example 7, the mixture was left to stand for 1 hour, and the aqueous phase catalyst was self-separated from the product. Extracting 5mL of upper layer water phase catalyst with dichloromethane, separating, adding the separated water phase catalyst to 6mL with fresh SLSRePd-3h solution with the same concentration, adding 1mmol (152 mg) of vanillin into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, replacing air with hydrogen, and separating at 1Initial H in MPa 2 The reaction was carried out at 70 ℃ for 2h under pressure and magnetic stirring at 400 rpm. The above steps were repeated 10 more times.
TABLE 2 sodium lignosulfonate Reducedly stabilized metal Pd nano particle catalyst SLSRePd-3h repeated use performance
Figure BDA0003769495220000042
The lower liquid product obtained in each separation was extracted with ethyl acetate, mixed with the above dichloromethane extract, and quantitatively analyzed by gas chromatography. The catalytic results obtained are shown in Table 2.
Comparative example 1
Adding 60mg of sodium lignosulfonate which has been vacuum-dried at 50 ℃ for 12 hours, 0.1mmol of sodium chloropalladate, 6mL of ultrapure water and 1mmol (152 mg) of vanillin into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing the kettle, replacing air with hydrogen, and then carrying out reaction at an initial H of 1MPa 2 The reaction was carried out at 50 ℃ for 1 hour under pressure and magnetic stirring at 400 rpm. After the reaction, the reaction mixture was extracted with ethyl acetate and quantitatively analyzed by gas chromatography, and the results are shown in Table 3.
Comparative example 2
60mg of sodium lignosulfonate which is dried in vacuum at 50 ℃ for 12 hours, 0.1mmol of sodium chloropalladate and 6mL of ultrapure water are added into a 25mL single-neck flask, the obtained solution is heated to 80 ℃ and is magnetically stirred and reacted at 400rpm for 3 hours to obtain an aqueous phase metal Pd nanoparticle catalyst SLSRePd-3h'.
Adding all SLSRePd-3H' aqueous phase catalyst prepared above and 1mmol (152 mg) of vanillin into a stainless steel high-pressure reaction kettle with polytetrafluoroethylene lining, sealing the kettle, replacing air with hydrogen, and performing initial H at 1MPa 2 The reaction was carried out at 50 ℃ for 1 hour under pressure and magnetic stirring at 400 rpm. After the reaction, the reaction mixture was extracted with ethyl acetate and quantitatively analyzed by gas chromatography, and the results are shown in Table 3.
Comparative example 3
Adding 60mg of sodium lignosulfonate which is dried in vacuum at 50 ℃ for 12 hours, 0.1mmol of sodium chloroplatinate and 6mL of ultrapure water into a 25mL single-neck flask, heating the obtained solution to 80 ℃, and reacting for 3 hours under magnetic stirring at 400rpm to obtain the water-phase metal Pt nanoparticle catalyst SLSREPT-3 hours.
Adding all SLSREPT-3H aqueous phase catalyst prepared above and 1mmol (152 mg) vanillin into a stainless steel autoclave with polytetrafluoroethylene lining, sealing the autoclave, replacing air with hydrogen, and reacting at 1MPa initial H 2 The reaction was carried out at 50 ℃ for 1 hour under pressure and magnetic stirring at 400 rpm. After the reaction, the reaction mixture was extracted with ethyl acetate and quantitatively analyzed by gas chromatography, and the results are shown in Table 3.
Comparative example 4
60mg of sodium lignosulfonate which is dried in vacuum at 50 ℃ for 12 hours, 0.1mmol of chloroplatinic acid and 6mL of ultrapure water are added into a 25mL single-neck flask, the obtained solution is heated to 80 ℃ and is magnetically stirred and reacted at 400rpm for 3 hours, and the water-phase metal Pt nanoparticle catalyst SLSREPT-3 hours' is obtained.
Adding all SLSREPT-3H' aqueous phase catalyst prepared above and 1mmol (152 mg) vanillin into a stainless steel autoclave with polytetrafluoroethylene lining, sealing the autoclave, replacing air with hydrogen, and adding hydrogen at 1MPa 2 The reaction was carried out at 50 ℃ for 1 hour under pressure and magnetic stirring at 400 rpm. After the reaction, the reaction mixture was extracted with ethyl acetate and quantitatively analyzed by gas chromatography, and the results are shown in Table 3.
Comparative example 5
Adding 60mg of sodium lignosulfonate which is dried in vacuum at 50 ℃ for 12 hours, 0.1mmol of ruthenium trichloride and 6mL of ultrapure water into a 25mL single-neck flask, heating the obtained solution to 80 ℃, and carrying out magnetic stirring reaction at 400rpm for 3 hours to obtain an aqueous phase metal Ru nanoparticle catalyst SLSReRu-3 hours.
Adding all SLSReRu-3H aqueous phase catalyst and 1mmol (152 mg) vanillin prepared above into a stainless steel high-pressure reaction kettle with polytetrafluoroethylene lining, sealing the kettle, replacing air with hydrogen, and reacting at 1MPa for initial H 2 The reaction was carried out at 50 ℃ for 1 hour under pressure and magnetic stirring at 400 rpm. After the reaction, the reaction mixture was extracted with ethyl acetate and quantitatively analyzed by gas chromatography, and the results are shown in Table 3.
Comparative example 6
Adding 60mg of sodium lignosulfonate which is dried in vacuum at 50 ℃ for 12 hours, 0.1mmol of silver nitrate and 6mL of ultrapure water into a 25mL single-neck flask, heating the obtained solution to 80 ℃, and carrying out magnetic stirring reaction at 400rpm for 3 hours to obtain an aqueous phase metal Ag nanoparticle catalyst SLSReAg-3 hours.
Adding all SLSReAg-3H aqueous phase catalyst and 1mmol (152 mg) vanillin prepared above into a stainless steel high pressure reaction kettle with polytetrafluoroethylene lining, sealing the kettle, replacing air with hydrogen, and reacting at 1MPa for initial H 2 The reaction was carried out at 50 ℃ for 1 hour under pressure and magnetic stirring at 400 rpm. After the reaction, the reaction mixture was extracted with ethyl acetate and quantitatively analyzed by gas chromatography, and the results are shown in Table 3.
Comparative example 7
60mg of Alkali Lignin (AL) which is dried in vacuum at 50 ℃ for 12h, 0.1mmol of sodium chloropalladate and 6mL of ultrapure water are added into a 25mL single-neck flask, and the obtained solution is heated to 80 ℃ and reacts for 3h under magnetic stirring at 400rpm to obtain an aqueous phase metal Pd nanoparticle catalyst ALrePd-3h.
Adding all the prepared ALrepD-3H aqueous phase catalyst and 1mmol (152 mg) vanillin into a stainless steel high-pressure reaction kettle with polytetrafluoroethylene lining, sealing the kettle, replacing air with hydrogen, and performing initial H at 1MPa 2 The reaction was carried out at 50 ℃ for 1 hour under pressure and magnetic stirring at 400 rpm. After the reaction, the reaction mixture was extracted with ethyl acetate and quantitatively analyzed by gas chromatography, and the results are shown in Table 3.
TABLE 3 catalytic vanillin hydrodeoxygenation by lignin derivative reduction-stable metal nanoparticles prepared under other conditions
Figure BDA0003769495220000061
Drawings
The attached drawings 1 are as follows from left to right: the appearance photos of (a) sodium lignosulfonate water solution, (b) sodium lignosulfonate and sodium chloropalladate mixed water solution in comparative example 1, (c) the system obtained when the sodium lignosulfonate and sodium chloropalladate mixed solution in example 1 reacts for 1 hour, and (d) the Pd metal nanoparticle catalyst SLSRePd-3 hours prepared in example 1.
FIG. 2 is an X-ray photoelectron spectroscopy (XPS) graph of the sodium lignosulfonate reduction-stabilized Pd metal nanoparticle catalyst SLSREPD-3h in example 1.
FIG. 3 is a Transmission Electron Microscope (TEM) photograph and a particle size distribution diagram of the sodium lignosulfonate reduction-stabilized Pd metal nanoparticle catalyst SLSRePd-3h in example 1.
FIG. 4 is a photograph showing the appearance of the self-separation effect of the reaction mixture after it was left to stand in example 11.

Claims (1)

1. A method for preparing 2-methoxy-4-methylphenol by catalyzing vanillin hydrodeoxygenation reaction through sodium lignosulfonate aqueous phase reduction and stable Pd nanoparticles is characterized in that: the method does not need to add other chemical reagents and organic solvents, adopts sodium lignosulfonate as a reducing agent and a stabilizing agent in aqueous solution to prepare Pd nano-particles for directly catalyzing vanillin hydrodeoxygenation reaction, and uses n (Vanillin) /n (Pd) Ratio of 10-300, initial H at 0.5-1.5MPa 2 Reacting for 1-2.5h at 50-80 ℃ under the magnetic stirring of 400rpm under the pressure, standing the mixture after the reaction is finished, and performing self-separation and layering, wherein the upper-layer aqueous phase catalyst is recycled; the preparation conditions of the aqueous phase catalytic system are as follows: preparing a solution according to the proportion of 0.6g of sodium lignosulfonate and 60mL of water per millimole of sodium chloropalladate, reacting for 3h at 40 ℃ under magnetic stirring of 400rpm to obtain black-brown opaque water-phase metal Pd nanoparticles, and diluting and using according to the proportion of the required catalyst and a substrate in the reaction.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115970723A (en) * 2023-01-19 2023-04-18 浙江工业大学 Preparation method and application of sulfur-modified activated carbon-loaded high-dispersion noble metal catalyst for selective hydrogenation of halogenated nitrobenzene
CN116715567A (en) * 2023-06-09 2023-09-08 青岛科技大学 Preparation method of creosol based on alkali lignin-based catalyst

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104262120A (en) * 2014-09-11 2015-01-07 浙江大学 Method for preparing 2-methoxy-4-methylphenol by catalyzing, hydrogenating and deoxidizing vanillin
US20150218073A1 (en) * 2012-09-07 2015-08-06 Kat2Biz Ab Catalytic reductive cleavage of a b-o-4 bond of ethers or polyethers such as lignin
US20160289150A1 (en) * 2013-10-27 2016-10-06 Purdue Research Foundation Catalytic biomass conversion methods, catalysts, and methods of making the same
CN106542972A (en) * 2016-10-30 2017-03-29 中南民族大学 A kind of method of normal temperature and pressure reducing carbonyl for methylene
US20170362162A1 (en) * 2014-12-15 2017-12-21 Organofuel Sweden Ab Synthesis of amides and amines from aldehydes or ketones by heterogeneous metal catalysis
CN108636423A (en) * 2018-05-17 2018-10-12 云南大学 A kind of preparation method of load type nano gold catalyst and application
CN109761938A (en) * 2018-12-15 2019-05-17 华南理工大学 A method of catalysis one step of 5 hydroxymethyl furfural reduction etherificate
US20220062880A1 (en) * 2020-06-09 2022-03-03 Korea Research Institute Of Chemical Technology Modified organometallic framework and catalyst for hydrogenation reaction including same
CN114524715A (en) * 2022-02-11 2022-05-24 河北工业大学 Method for directionally hydrogenating carbonyl compound

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150218073A1 (en) * 2012-09-07 2015-08-06 Kat2Biz Ab Catalytic reductive cleavage of a b-o-4 bond of ethers or polyethers such as lignin
US20160289150A1 (en) * 2013-10-27 2016-10-06 Purdue Research Foundation Catalytic biomass conversion methods, catalysts, and methods of making the same
CN104262120A (en) * 2014-09-11 2015-01-07 浙江大学 Method for preparing 2-methoxy-4-methylphenol by catalyzing, hydrogenating and deoxidizing vanillin
US20170362162A1 (en) * 2014-12-15 2017-12-21 Organofuel Sweden Ab Synthesis of amides and amines from aldehydes or ketones by heterogeneous metal catalysis
CN106542972A (en) * 2016-10-30 2017-03-29 中南民族大学 A kind of method of normal temperature and pressure reducing carbonyl for methylene
CN108636423A (en) * 2018-05-17 2018-10-12 云南大学 A kind of preparation method of load type nano gold catalyst and application
CN109761938A (en) * 2018-12-15 2019-05-17 华南理工大学 A method of catalysis one step of 5 hydroxymethyl furfural reduction etherificate
US20220062880A1 (en) * 2020-06-09 2022-03-03 Korea Research Institute Of Chemical Technology Modified organometallic framework and catalyst for hydrogenation reaction including same
CN114524715A (en) * 2022-02-11 2022-05-24 河北工业大学 Method for directionally hydrogenating carbonyl compound

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DAN-DAN LI ET AL.: "Pd Nanoparticles Supported on Cellulose as a Catalyst for Vanillin Conversion in Aqueous Media", J. ORG. CHEM., vol. 83, 31 December 2018 (2018-12-31), pages 7534 - 7538 *
HAO HUANG ET AL.: "Synergy Effects between Oxygen Groups and Defects in Hydrodeoxygenation of Biomass over a Carbon Nanosphere Supported Pd Catalyst", ACS SUSTAINABLE CHEMISTRY & ENGINEERING, vol. 8, 31 December 2020 (2020-12-31), pages 15998 - 16009 *
JIANSU RAN ET AL.: ""Promotion of sulfonic acid groups on biomass carbons loading ultrafine palladium nanoparticles for the efficient hydrodeoxygenation of vanillin in water"", CURRENT RESEARCH IN GREEN AND SUSTAINABLE CHEMISTRY, vol. 5, 31 December 2021 (2021-12-31), pages 100230 *
JIANSU RAN ET AL.: "Significant Promotion of Carboxyl Groups in Palladium Nanoparticles-Supported Biomass Carbon Catalysts for Efficient Low-Temperature Hydrodeoxygenation of Lignin Derivatives in Water", ACS SUSTAINABLE CHEM. ENG, vol. 10, 25 May 2022 (2022-05-25), pages 7277 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115970723A (en) * 2023-01-19 2023-04-18 浙江工业大学 Preparation method and application of sulfur-modified activated carbon-loaded high-dispersion noble metal catalyst for selective hydrogenation of halogenated nitrobenzene
CN116715567A (en) * 2023-06-09 2023-09-08 青岛科技大学 Preparation method of creosol based on alkali lignin-based catalyst
CN116715567B (en) * 2023-06-09 2024-05-28 青岛科技大学 Preparation method of creosol based on alkali lignin-based catalyst

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