CN108947783A - A kind of method that molybdenum Catalytic lignin is degraded to fragrant monomer - Google Patents
A kind of method that molybdenum Catalytic lignin is degraded to fragrant monomer Download PDFInfo
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- CN108947783A CN108947783A CN201710351325.8A CN201710351325A CN108947783A CN 108947783 A CN108947783 A CN 108947783A CN 201710351325 A CN201710351325 A CN 201710351325A CN 108947783 A CN108947783 A CN 108947783A
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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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
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Abstract
A kind of method that molybdenum Catalytic lignin is degraded to fragrant monomer, this method are degraded using molecular oxygen as oxygen source by catalyst lignin oxidation of base metal molybdenum compound.In this method, catalytic oxidation system composition is simple, green, and operating condition is mild, the high income of fragrant monomer (predominantly aromatic aldehyde, aromatic ketone, aromatic esters) in catabolite；Possibility is provided for the higher value application of protolignin or even lignocellulosic.
Description
Technical field
The present invention relates to the fields that biomass is converted into organic chemicals comprehensive utilization, specifically: by lignocellulosic
Or lignin carries out catalyzing oxidizing degrading, obtains the fragrant small molecule list of the high added values such as aromatic aldehyde, aromatic ketone, aromatic esters
Body compound, to realize effective higher value application of lignin.
Background technique
The problems such as conventional fossils resource such as coal, petroleum increasingly consumes, environmental pollution is increasingly aggravated, and renewable life is developed and used
Physical resources realize that sustainable development is the emphasis and difficult point of contemporary society's urgent need to resolve.Biomass resource is widely present in nature
It is rich reserves, renewable in boundary.Plant biomass chief component includes cellulose, hemicellulose, lignin etc., wherein
The content of lignin is about 15-30wt% or so.Relative to cellulose, hemicellulose, lignin is mainly as pulping and paper-making row
The offal treatment of industry, not only waste of resource, also pollutes environment.Lignin be can directly provide in nature so far it is large
The renewable resource of natural aroma compound.The method for developing simple, efficient lignin degrading, to the high level for realizing lignin
Change using most important.
Lignin is a kind of structure is complicated various, amorphous and high polymeric three-dimensional netted macromolecular, mainly by benzene
Propane structural unit is keyed by C-C key or C-O.It is broken the C-C key being connected or C-O key is to realize lignin conversion
For the key point of the aromatic compound of high added value.Reported lignin conversion method, as thermal cracking, it is overcritical conversion,
Acid and alkali hydrolysis etc., the disadvantages such as that there is operating conditions is harsh, target fragrant monomer yield is low.Complicated in view of lignin itself
Small molecule intermediates obtained in architectural characteristic and degradation process are easy to polymerize again, efficient, highly selective lignin degrading
Obtain the difficult point place that fragrant monomer is still current research.
Summary of the invention
It is an object of that present invention to provide a kind of method that molybdenum Catalytic lignin is degraded to fragrant monomer, this method is to divide
Sub- oxygen is oxygen source, is degraded by catalyst lignin oxidation of base metal molybdenum compound.
Method provided by the present invention, degradation system is simple, green, and operating condition is mild, and aromatic compound is (main in product
To include aromatic aldehyde, aromatic ketone, aromatic esters) high income；For mentioning for the higher value application of lignin or even lignocellulosic
Having supplied may.
The oxidation degradation method of Catalytic lignin provided by the invention, the raw material wood element, including sawdust, shell, straw
Protolignin and alkali lignin, sulfonate lignin, dealkalize lignin in stalk, organic solvent solution lignin.
The catalyst is base metal molybdenum compound, including molybdenum trioxide, molybdenum disulfide, molybdenum pentachloride, sodium molybdate, second
One or more of acyl acetone oxygen molybdenum；Catalyst amount is the 10-100wt% of raw material inventory, preferentially selects 20-
50wt%.
The method of the Catalytic lignin oxidative degradation, reaction condition are as follows: oxygen source is oxygen, partial pressure of oxygen 0.2-
2.0MPa preferentially selects 0.5-1.5MPa；Temperature is 80-250 DEG C, preferential 100-200 DEG C of selection；Reaction time is 2-10h, excellent
First select 2-12h.
Solvent for use is one or more of methanol, ethyl alcohol, ethyl acetate, ethylene glycol in the reaction；Solvent
Mass ratio with lignin is 10-100.
In the catalyzing oxidizing degrading reaction, obtained fragrant small molecule monomer mainly includes aromatic aldehyde, aromatic ketone, fragrance
Acid esters, total fragrant monomer yield is up to 60wt% or more.
The method of lignin degrading provided by the invention uses simple base metal molybdenum compound for catalyst, mildly
Under the conditions of can by alkali lignin, sulfonate lignin, dealkalize lignin, organic solvent solution lignin even sawdust, shell, straw
Protolignin's Direct Catalytic Oxidation degradation in stalk, obtains aromatic aldehyde, aromatic ketone, aromatic acid (ester) small molecule monomer, belongs to
It is high valuable chemicals resource utilization by the lignin conversion in biomass resource, meets the demand of sustainable development.
Specific embodiment
Protolignin's (hardwood, cork, shell, stalk) first crushes through pulverizer, and ball mill mechanical treatment obtains particle
About 40 mesh of diameter is spare.
Embodiment 1:
By 1.0g poplar sawdust, 0.5g acetylacetone,2,4-pentanedione oxygen molybdenum, 30mL methanol is added in 100mL reaction kettle, and oxygenation is extremely
1.0MPa, keeps 6h by 180 DEG C of temperature.It is cooled to room temperature, it is qualitative to product is compared using GC-MS and with standard substance, it utilizes
Quantified by external standard method analysis；Ratio i.e. its yield of the quality of obtained each product and the middle lignin quality that initially feeds intake.
Fragrant monomer mainly includes parahydroxyben-zaldehyde, P-hydroxybenzoic acid, methyl p-hydroxybenzoate, vanilla in product
Aldehyde, vanillone, vanillic acid, vanillic acid methyl esters, syringaldehyde, syringic acid, NSC 611398.The receipts of total fragrant small molecule compound
Rate is 68wt%.
Embodiment 2:
By 1.0g beech sawdust, 0.5g molybdenum trioxide, 30mL ethyl alcohol is added in 100mL reaction kettle, oxygenation to 1.0MPa, temperature
150 DEG C of degree keeps 5h.It is cooled to room temperature, qualitative and quantitative analysis is carried out to reaction solution using 1 method of embodiment.
Fragrant small molecule mainly includes parahydroxyben-zaldehyde, P-hydroxybenzoic acid, ethyl-para-hydroxybenzoate, perfume (or spice) in product
Oxalaldehyde, vanillone, vanillic acid, ethyl vanillate, syringaldehyde, syringic acid, Ethyl syringate.Total fragrant small molecule compound
Yield is 62wt%.
Embodiment 3:
By 1.0g sulfonate lignin, 0.2g sodium molybdate, 30mL ethylene glycol is added in 100mL reaction kettle, and oxygenation is extremely
1.0MPa, keeps 10h by 120 DEG C of temperature.It is cooled to room temperature, qualitative and quantitative analysis is carried out to reaction solution using 1 method of embodiment.
Fragrant small molecule mainly includes parahydroxyben-zaldehyde, P-hydroxybenzoic acid, ethyl-para-hydroxybenzoate, perfume (or spice) in product
Oxalaldehyde, vanillone, vanillic acid, ethyl vanillate, syringaldehyde, syringic acid, Ethyl syringate.Total fragrant small molecule compound
Yield is 60wt%.
Embodiment 4:
By 1.0g alkali lignin, 1.0g acetylacetone,2,4-pentanedione oxygen molybdenum, 30mL methanol is added in 100mL reaction kettle, and oxygenation is extremely
1.5MPa, keeps 3h by 160 DEG C of temperature.It is cooled to room temperature, qualitative and quantitative analysis is carried out to reaction solution using 1 method of embodiment.
Fragrant small molecule mainly includes parahydroxyben-zaldehyde, P-hydroxybenzoic acid, methyl p-hydroxybenzoate, perfume (or spice) in product
Oxalaldehyde, vanillone, vanillic acid, vanillic acid methyl esters, syringaldehyde, syringic acid, NSC 611398.Total fragrant small molecule compound
Yield is 64wt%.
Embodiment 5:
By 1.0g poplar sawdust, 1.0g acetylacetone,2,4-pentanedione oxygen molybdenum, 30mL ethyl acetate is added in 100mL reaction kettle, and oxygenation is extremely
1.0MPa 200 DEG C of temperature, keeping 3h.It is cooled to room temperature, qualitative and quantitative analysis is carried out to reaction solution using 1 method of embodiment.
Fragrant small molecule mainly includes parahydroxyben-zaldehyde, P-hydroxybenzoic acid, ethyl-para-hydroxybenzoate, perfume (or spice) in product
Oxalaldehyde, vanillone, vanillic acid, ethyl vanillate, syringaldehyde, syringic acid, Ethyl syringate.Total fragrant small molecule compound
Yield is 61wt%.
Embodiment 6:
By 1.0g beech sawdust, 0.8g molybdenum trioxide, 30mL methanol is added in 100mL reaction kettle, oxygenation to 1.5MPa, temperature
160 DEG C of degree keeps 3h.It is cooled to room temperature, qualitative and quantitative analysis is carried out to reaction solution using 1 method of embodiment.
Fragrant small molecule mainly includes parahydroxyben-zaldehyde, P-hydroxybenzoic acid, methyl p-hydroxybenzoate, perfume (or spice) in product
Oxalaldehyde, vanillone, vanillic acid, vanillic acid methyl esters, syringaldehyde, syringic acid, NSC 611398.Total fragrant small molecule compound
Yield is 66wt%.
Embodiment 7:
By 1.0g sulfonate lignin, 0.5g molybdenum disulfide, 30mL ethyl alcohol is added in 100mL reaction kettle, and oxygenation is extremely
1.0MPa, keeps 4h by 160 DEG C of temperature.It is cooled to room temperature, qualitative and quantitative analysis is carried out to reaction solution using 1 method of embodiment.
Fragrant small molecule mainly includes parahydroxyben-zaldehyde, P-hydroxybenzoic acid, ethyl-para-hydroxybenzoate, perfume (or spice) in product
Oxalaldehyde, vanillone, vanillic acid, ethyl vanillate, syringaldehyde, syringic acid, Ethyl syringate.Total fragrant small molecule compound
Yield is 62wt%.
Embodiment 8:
By 1.0g alkali lignin, 0.8g molybdenum disulfide, 30mL ethyl acetate is added in 100mL reaction kettle, and oxygenation is extremely
1.5MPa, keeps 3h by 200 DEG C of temperature.It is cooled to room temperature, qualitative and quantitative analysis is carried out to reaction solution using 1 method of embodiment.
Fragrant small molecule mainly includes parahydroxyben-zaldehyde, P-hydroxybenzoic acid, ethyl-para-hydroxybenzoate, perfume (or spice) in product
Oxalaldehyde, vanillone, vanillic acid, ethyl vanillate, syringaldehyde, syringic acid, Ethyl syringate.Total fragrant small molecule compound
Yield is 65wt%.
Claims (8)
1. a kind of method that molybdenum Catalytic lignin is degraded to fragrant monomer, it is characterised in that: this method is using molecular oxygen as oxygen
Source, using molybdenum compound as catalyst, fcc raw material lignin oxidation is degraded to fragrant monomer.
2. according to the method for claim 1, it is characterised in that: the raw material wood element includes one of following or two kinds
More than, including one of sawdust, shell, stalk or two kinds or more protolignin and alkali lignin, sulfonate it is wooden
One of element, dealkalize lignin, organic solvent solution lignin or two kinds or more.
3. according to the method for claim 1, it is characterised in that: the catalyst is base metal molybdenum compound, including three
One or more of molybdenum oxide, molybdenum disulfide, molybdenum pentachloride, sodium molybdate, acetylacetone,2,4-pentanedione oxygen molybdenum.
4. according to method described in claim 1 or 3, it is characterised in that: catalyst amount is the 10- of raw material inventory
100wt% preferentially selects 20-50wt%.
5. according to the method for claim 1, it is characterised in that: molecular oxygen is oxygen or oxygen-containing gas (such as air), reaction
Partial pressure of oxygen is 0.2-2.0MPa in system, preferably selects 0.5-1.5MPa；Temperature is 80-250 DEG C, preferably selects 100-200 DEG C；
Reaction time is 2-20h, preferably selects 2-12h.
6. according to the method for claim 1, it is characterised in that: reaction carries out in a solvent, and solvent for use is methanol, second
One or more of alcohol, ethyl acetate, ethylene glycol；The mass ratio of solvent and lignin is 10-100.
7. according to the method for claim 1, it is characterised in that: in the catalyzing oxidizing degrading reaction, obtained fragrance is small
Molecular compound mainly includes one of aromatic aldehyde, aromatic ketone, aromatic acid, aromatic ester or two kinds or more, total fragrant monomer
Yield is up to 60wt% or more.
8. according to the method for claim 7, it is characterised in that:
The aromatic aldehyde is one of parahydroxyben-zaldehyde, vanillic aldehyde, syringaldehyde or two kinds or more；
The aromatic ketone is one of vanillone, syringone or two kinds or more；
The aromatic acid is one of P-hydroxybenzoic acid, vanillic acid, syringic acid or two kinds or more；The aromatic ester is to hydroxyl
One of yl benzoic acid ester, vanilla acid esters, cloves acid esters or two kinds or more.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110078877A (en) * | 2019-04-26 | 2019-08-02 | 福州大学 | A kind of methods and applications preparing dispersing agent using lignin degradation products |
| CN110922314A (en) * | 2019-12-06 | 2020-03-27 | 玉林师范学院 | Method for preparing aromatic aldehyde by catalytic oxidation of lignin degradation |
| CN111978164A (en) * | 2019-05-21 | 2020-11-24 | 中国科学院大连化学物理研究所 | Method for preparing aromatic aldehyde by visible light catalytic oxidation of lignin |
| CN112979414A (en) * | 2019-12-13 | 2021-06-18 | 中国科学院大连化学物理研究所 | Method for preparing aromatic compound from lignin |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102115432A (en) * | 2010-12-30 | 2011-07-06 | 江南大学 | Method for preparing and separating p-hydroxybenzaldehyde, vanillin and syringaldehyde from lignin |
| CN102875343A (en) * | 2012-10-31 | 2013-01-16 | 南京林业大学 | Method for preparing aromatic aldehyde compound by catalyzing and degrading lignin with loaded solid acid |
| CN103059067A (en) * | 2013-01-15 | 2013-04-24 | 淮阴师范学院 | Method for preparing aromatic aldehyde from lignocellulose hydrolysis residue by two-step process |
| CN103910903A (en) * | 2013-01-08 | 2014-07-09 | 天津大学 | Application of molybdenum-based catalyst to prepare organic chemicals from lignin |
| CN105669337A (en) * | 2014-11-19 | 2016-06-15 | 中国科学院大连化学物理研究所 | Method for converting lignin and model compound thereof |
-
2017
- 2017-05-18 CN CN201710351325.8A patent/CN108947783B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102115432A (en) * | 2010-12-30 | 2011-07-06 | 江南大学 | Method for preparing and separating p-hydroxybenzaldehyde, vanillin and syringaldehyde from lignin |
| CN102875343A (en) * | 2012-10-31 | 2013-01-16 | 南京林业大学 | Method for preparing aromatic aldehyde compound by catalyzing and degrading lignin with loaded solid acid |
| CN103910903A (en) * | 2013-01-08 | 2014-07-09 | 天津大学 | Application of molybdenum-based catalyst to prepare organic chemicals from lignin |
| CN103059067A (en) * | 2013-01-15 | 2013-04-24 | 淮阴师范学院 | Method for preparing aromatic aldehyde from lignocellulose hydrolysis residue by two-step process |
| CN105669337A (en) * | 2014-11-19 | 2016-06-15 | 中国科学院大连化学物理研究所 | Method for converting lignin and model compound thereof |
Non-Patent Citations (2)
| Title |
|---|
| DENG HAIBO等: "Catalysis of Cu-Doped Co-Based Perovskite-Type Oxide in Wet Oxidation of Lignin To Produce Aromatic Aldehydes", 《ENERGY FUELS》 * |
| TOBIAS VOITL等: "Oxidation of lignin using aqueous polyoxometalates in the presence of alcohols", 《CHEMSUSCHEM》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110078877A (en) * | 2019-04-26 | 2019-08-02 | 福州大学 | A kind of methods and applications preparing dispersing agent using lignin degradation products |
| CN110078877B (en) * | 2019-04-26 | 2021-07-27 | 福州大学 | Method for preparing dispersant by using lignin degradation product and application |
| CN111978164A (en) * | 2019-05-21 | 2020-11-24 | 中国科学院大连化学物理研究所 | Method for preparing aromatic aldehyde by visible light catalytic oxidation of lignin |
| CN111978164B (en) * | 2019-05-21 | 2022-10-14 | 中国科学院大连化学物理研究所 | Method for preparing aromatic aldehyde by visible light catalytic oxidation of lignin |
| CN110922314A (en) * | 2019-12-06 | 2020-03-27 | 玉林师范学院 | Method for preparing aromatic aldehyde by catalytic oxidation of lignin degradation |
| CN112979414A (en) * | 2019-12-13 | 2021-06-18 | 中国科学院大连化学物理研究所 | Method for preparing aromatic compound from lignin |
| CN112979414B (en) * | 2019-12-13 | 2022-01-14 | 中国科学院大连化学物理研究所 | Method for preparing aromatic compound from lignin |
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