CN107857696A - The method that catalysis oxidation lignin prepares high-purity vanillic aldehyde - Google Patents
The method that catalysis oxidation lignin prepares high-purity vanillic aldehyde Download PDFInfo
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- CN107857696A CN107857696A CN201711040638.8A CN201711040638A CN107857696A CN 107857696 A CN107857696 A CN 107857696A CN 201711040638 A CN201711040638 A CN 201711040638A CN 107857696 A CN107857696 A CN 107857696A
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- Prior art keywords
- lignin
- vanillic aldehyde
- purity
- catalysis oxidation
- rhenium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses the method that catalysis oxidation lignin prepares high-purity vanillic aldehyde, lignin is mixed Yu Rhenium bases load oxide catalyst, add phenol stirring, dissolving, lignin is degraded under 1~3MPa of oxygen pressure reaction condition, the catabolite based on vanillic aldehyde is obtained, separation is carried out to product and obtains vanillic aldehyde.The present invention is raw material with lignin, is catalyst by the use of phenol as solvent , Yong Rhenium bases load oxide, preparation condition is gentle, reduces the requirement difficulty of preparation condition, and cost is low, and power consumption is few, Environmental Safety.
Description
Technical field
The present invention relates to a kind of method for preparing vanillic aldehyde, and in particular to catalysis oxidation lignin prepares high-purity vanillic aldehyde
Method.
Background technology
Vanillic aldehyde (3-methoxy-4-hydroxybenzaldehyde) is always what natural herb seasoned in food for centuries
Main component.Nowadays, it is widely used in industry-by-industry.In the food industry, it be used as ice cream, beverage, chocolate,
Roasting candy and flavor enhancement；A kind of food preservative is also served as used in sausage, in flavoring, etc..In cosmetic industry, it
Perfume and face cream as flavor component；In chemical industry, as defoamer, vulcanizing agent and precursor；In medical industry
As odor masking agent.Recently, vanillic aldehyde is used also as synthesis of all kinds of intermediates etc., for example, levodopa, ethyldopa,
The various pharmaceutical synthesis such as papaverine.
Vanillic aldehyde can be produced by vanilla bean, petroleum derivation product and lignin, typically from lignin as preparation vanilla
The raw material of aldehyde, because lignin is a kind of a large amount of renewable physical resources and has long-term sustainable；But prepared in lignin
The production procedure of vanillic aldehyde is complicated, while the vanillic aldehyde for having vast number produces, and the vanillic aldehyde later separation of generation is considerably complicated.
The content of the invention
The technical problems to be solved by the invention are that existing lignin prepares and can produce substantial amounts of perfume (or spice) in vanillic aldehyde simultaneously
Lan Su, cause vanillic aldehyde later separation difficult, and it is an object of the present invention to provide the method that catalysis oxidation lignin prepares high-purity vanillic aldehyde,
Solves the problem of amount of by-products is big in lignin catabolite, vanillic aldehyde later separation difficulty.
The present invention is achieved through the following technical solutions：
The method that catalysis oxidation lignin prepares high-purity vanillic aldehyde, lignin Yu Rhenium bases load oxide catalyst are mixed
Close, add phenol stirring, dissolving, lignin is degraded under 1~3MPa of oxygen pressure reaction condition, is obtained with vanillic aldehyde
Based on catabolite, to product carry out separation obtain vanillic aldehyde.
It is raw material with lignin, is catalyst by the use of phenol as solvent , Yong Rhenium bases load oxide, preparation condition is gentle,
The requirement difficulty of preparation condition is reduced, cost is low, and power consumption is few, Environmental Safety；In the product, the selectivity of vanillic aldehyde is 90-
97%, the high selectivity significantly reduces the technological requirement of vanillic aldehyde separating-purifying in product, solves vanillic aldehyde and subsequently divides
The problem of from difficulty, and phenol as solvent and can divide as catalyst Gu Ti Rhenium bases load oxide from product
From, reuse, the saving energy, and environmental pollution will not be caused.The present invention is that one kind not only has economic value but also green ring
That protects prepares vanillic aldehyde new method from lignin.
The reaction condition also includes 80-120 DEG C of reaction temperature.With the reduction of reaction temperature, the production of vanillic aldehyde yield
Amount reduces, and the selectivity of vanillic aldehyde gradually reduces, and when temperature is 80 DEG C, the selectivity of vanillic aldehyde is close to 90%, far above existing
The selectivity of vanillic aldehyde in technology, in order to reduce the technological requirement of vanillic aldehyde separating-purifying in product, the selection of vanillic aldehyde
Property reach 90% and the preparation condition of the above be optimal preparation condition.
Suo Shu Rhenium bases load oxide catalyst Wei Rhenium base load aluminum trioxide catalysts.Rhenium bases load alundum (Al2O3)
As catalyst, vanillic aldehyde selectively increases to 95%, in the prior art without so high vanillic aldehyde selectivity；Rhenium bases load
Aluminum trioxide catalyst can also recycle.
The lignin degradation time is 0.5-1 hours.The degradation time of lignin is less than lignin of the prior art
Degradation time, production efficiency are high.
The lignin includes appointing in enzymolysis xylogen, alkali lignin, sodium lignin sulfonate, organic solvent type lignin
The mixture for one or more of anticipating.
The present invention compared with prior art, has the following advantages and advantages：
1st, it is raw material that catalysis oxidation lignin of the present invention, which prepares the method for high-purity vanillic aldehyde with lignin, by the use of phenol as
Solvent , is catalyst Yong Rhenium bases load oxide, and preparation condition is gentle, reduces the requirement difficulty of preparation condition, and cost is low, consumption
Can be few, Environmental Safety；
2nd, in the product, the selectivity of vanillic aldehyde is high for the method for catalysis oxidation lignin preparation high-purity vanillic aldehyde of the present invention
In 90-97%, the high selectivity significantly reduces the technological requirement of vanillic aldehyde separating-purifying in product, after solving vanillic aldehyde
It is continuous to separate the problem of difficult；
3rd, phenol and conduct catalyst Gu Ti Rhenium in the method for catalysis oxidation lignin preparation high-purity vanillic aldehyde of the present invention
Base load oxide can separate from product, reuse, save the energy.
Embodiment
For the object, technical solutions and advantages of the present invention are more clearly understood, with reference to embodiment, the present invention is made
Further to describe in detail, exemplary embodiment of the invention and its explanation are only used for explaining the present invention, are not intended as to this
The restriction of invention.
Embodiment 1
The method that catalysis oxidation lignin of the present invention prepares high-purity vanillic aldehyde, lignin Yu Rhenium bases load oxide are urged
Agent mix, add phenol stirring, dissolving, lignin is degraded under 1~3MPa of oxygen pressure reaction condition, obtain with
Catabolite based on vanillic aldehyde, separation is carried out to product and obtains vanillic aldehyde.The reaction condition is anti-also including 80-120 DEG C
Answer temperature；Suo Shu Rhenium bases load oxide catalyst Wei Rhenium base load aluminum trioxide catalysts；The lignin degradation time
For 0.5-1 hours；The lignin is included in enzymolysis xylogen, alkali lignin, sodium lignin sulfonate, organic solvent type lignin
Any one or a few mixture.
With the reduction of reaction temperature, vanillic aldehyde yield yield reduction, the selectivity of vanillic aldehyde gradually reduces, temperature 80
DEG C when, the selectivity of vanillic aldehyde is close to 90%, far above the selectivity of vanillic aldehyde of the prior art, in order to reduce in product
The technological requirement of vanillic aldehyde separating-purifying, the selectivity of vanillic aldehyde reach 90% and the preparation condition of the above be optimal to prepare bar
Part.Rhenium bases load alundum (Al2O3) is used as catalyst, and vanillic aldehyde selectively increases to 95%, in the prior art without so high
Vanillic aldehyde selectivity；Rhenium bases load aluminum trioxide catalyst can also recycle.The degradation time of lignin is less than existing
Lignin degradation time in technology, production efficiency are high.
It is raw material with lignin, is catalyst by the use of phenol as solvent , Yong Rhenium bases load oxide, preparation condition is gentle,
The requirement difficulty of preparation condition is reduced, cost is low, and power consumption is few, Environmental Safety；In the product, the selectivity of vanillic aldehyde is 90-
97% is selective higher than the vanillic aldehyde of the alkaline oxygenated lignin of nitrobenzene, and the alkaline oxygenated lignin of nitrobenzene is obtained from lignin
The classical way of vanillic aldehyde；The high selectivity of vanillic aldehyde significantly reduces the work of vanillic aldehyde separating-purifying in product in the present invention
Skill requirement, solves the problems, such as vanillic aldehyde later separation difficulty, and phenol and conduct catalyst Gu Ti Rhenium bases as solvent
Load oxide can separate from product, reuse, and save the energy, and will not cause environmental pollution.The present invention is
It is a kind of that not only there is economic value but also green prepared vanillic aldehyde new method from lignin.
Embodiment 2
The method that catalysis oxidation lignin of the present invention prepares high-purity vanillic aldehyde, by the oxidation two of lignin Yu Rhenium bases load three
Al catalysts mix, and add phenol stirring, dissolving, oxygen pressure 2MPa, 80 DEG C of reaction temperatures reaction condition under lignin
0.5-1 hours of degrading are carried out, obtain the catabolite based on vanillic aldehyde, separation is carried out to product and obtains vanillic aldehyde；The wood
Quality includes any one or a few in enzymolysis xylogen, alkali lignin, sodium lignin sulfonate, organic solvent type lignin
Mixture.The housing choice behavior 90%-92.5% of vanillic aldehyde in the present embodiment.
Embodiment 3
As different from Example 2, the reaction temperature is 120 DEG C, the housing choice behavior 95%- of vanillic aldehyde in the present embodiment
97%.
Comparative example 1
By lignin and Fe2O3/Al2O3Catalyst mix, add phenol stirring, dissolving, oxygen pressure 2MPa, 120 DEG C
Lignin carries out 0.5-1 hours of degrading under the reaction condition of reaction temperature, the catabolite based on vanillic aldehyde is obtained, to product
Carry out separation and obtain vanillic aldehyde；The lignin includes enzymolysis xylogen, alkali lignin, sodium lignin sulfonate, organic solvent type
Any one or a few mixture in lignin.The selectivity of vanillic aldehyde is 63-64% in this comparative example, less than the present invention
Vanillic aldehyde selectivity.
Comparative example 2
Lignin is mixed with Pd/C catalyst, adds phenol stirring, dissolving, in oxygen pressure 2MPa, 120 DEG C of reaction temperature
Lignin carries out 0.5-1 hours of degrading under the reaction condition of degree, obtains the catabolite based on vanillic aldehyde, product is divided
From acquisition vanillic aldehyde；The lignin includes enzymolysis xylogen, alkali lignin, sodium lignin sulfonate, organic solvent type lignin
In any one or a few mixture.The housing choice behavior 85-86% of vanillic aldehyde in this comparative example, less than the vanilla of the present invention
The selectivity of aldehyde.
Above-described embodiment, the purpose of the present invention, technical scheme and beneficial effect are carried out further
Describe in detail, should be understood that the embodiment that the foregoing is only the present invention, be not intended to limit the present invention
Protection domain, within the spirit and principles of the invention, any modification, equivalent substitution and improvements done etc., all should include
Within protection scope of the present invention.
Claims (5)
1. the method that catalysis oxidation lignin prepares high-purity vanillic aldehyde, it is characterised in that lignin Yu Rhenium bases are loaded and aoxidized
Thing catalyst mixes, and adds phenol stirring, dissolving, lignin is degraded under 1~3MPa of oxygen pressure reaction condition, is obtained
To the catabolite based on vanillic aldehyde, separation is carried out to product and obtains vanillic aldehyde.
2. the method that catalysis oxidation lignin according to claim 1 prepares high-purity vanillic aldehyde, it is characterised in that described
Reaction condition also includes 80-120 DEG C of reaction temperature.
3. the method that catalysis oxidation lignin according to claim 1 prepares high-purity vanillic aldehyde, it is characterised in that described
Rhenium bases load oxide catalyst Wei Rhenium base load aluminum trioxide catalysts.
4. the method that catalysis oxidation lignin according to claim 2 prepares high-purity vanillic aldehyde, it is characterised in that described
The lignin degradation time is 0.5-1 hours.
5. the method that catalysis oxidation lignin according to claim 1 prepares high-purity vanillic aldehyde, it is characterised in that described
Lignin includes any one or a few in enzymolysis xylogen, alkali lignin, sodium lignin sulfonate, organic solvent type lignin
Mixture.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711040638.8A CN107857696A (en) | 2017-10-31 | 2017-10-31 | The method that catalysis oxidation lignin prepares high-purity vanillic aldehyde |
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| CN201711040638.8A CN107857696A (en) | 2017-10-31 | 2017-10-31 | The method that catalysis oxidation lignin prepares high-purity vanillic aldehyde |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102548935A (en) * | 2009-10-13 | 2012-07-04 | 环球油品公司 | Process for lignin conversion to chemicals or fuels with h2 generated from lignin depolymerization products |
| CN104744204A (en) * | 2015-02-04 | 2015-07-01 | 华东理工大学 | Method for preparing aromatic hydrocarbon by carrying out catalytic hydrodeoxygenation on lignin |
| CN105237371A (en) * | 2015-11-13 | 2016-01-13 | 南京工业大学 | Method for preparing vanillin through catalytic oxidation degradation of lignin |
| WO2017171652A1 (en) * | 2016-03-30 | 2017-10-05 | Agency For Science, Technology And Research | Process for the depolymerization of lignin under neutral oxidative conditions |
-
2017
- 2017-10-31 CN CN201711040638.8A patent/CN107857696A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102548935A (en) * | 2009-10-13 | 2012-07-04 | 环球油品公司 | Process for lignin conversion to chemicals or fuels with h2 generated from lignin depolymerization products |
| CN104744204A (en) * | 2015-02-04 | 2015-07-01 | 华东理工大学 | Method for preparing aromatic hydrocarbon by carrying out catalytic hydrodeoxygenation on lignin |
| CN105237371A (en) * | 2015-11-13 | 2016-01-13 | 南京工业大学 | Method for preparing vanillin through catalytic oxidation degradation of lignin |
| WO2017171652A1 (en) * | 2016-03-30 | 2017-10-05 | Agency For Science, Technology And Research | Process for the depolymerization of lignin under neutral oxidative conditions |
Non-Patent Citations (1)
| Title |
|---|
| JIZHONG LUO,PRAWIRASATYA MELISSA,WENGUANG ZHAO ET AL.: "Selective Lignin Oxidation towards Vanillin in Phenol Media", 《CHEMISTRYSELECT》 * |
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