CN104177447A - Method for preparing phenolic chemicals by catalyzing degradation of lignin with carbon-based solid acid - Google Patents
Method for preparing phenolic chemicals by catalyzing degradation of lignin with carbon-based solid acid Download PDFInfo
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Abstract
The invention provides a method for preparing phenolic chemicals by catalyzing degradation of lignin with carbon-based solid acid. The method comprises the following steps: by taking lignin as a raw material, a carbon-based solid acid as a catalyst and a water phase as a reaction solvent, putting lignin, carbon-based solid acid and water into a high-pressure reaction kettle; and carrying out warming reaction under the protection of an inert gas, and then extracting by using ethyl acetate, and performing vacuum evaporation so as to obtain the phenolic chemicals, wherein used carbon-based solid acid is prepared by using the lignin as the raw material in an inorganic acid environment; and the lignin raw material for carbon-based solid acid is alkali lignin, organic lignin, zymolytic lignin residue or hydrolytic lignin residue. The phenol yield can be up to 53%, the relative selectivity of guaiacol aromatic products can be up to 70%, the technique disclosed by the invention is simple and environmental friendly, available in raw materials and low in demands on equipment, and does not need to use a concentrated acid with strong corrosivity, and compared with the prior art, the method has outstanding advantages.
Description
Technical field
The present invention relates to utilize xylogen to prepare the method for phenols chemical; Particularly relate to a kind of take carbon-based solid acid as catalyzer, in aqueous phase system direct catalysis lignin degradation, the method for producing phenols chemical.
Background technology
Non-renewable and a large amount of consumption of fossil resource causes the shortage of energy chemical and series of environmental problems.Development and utilization renewable resources, becomes the inexorable trend of social development.Xylogen, as the chief component of lignocellulose-like biomass, is the Main By product of lignocellulose biomass by hydrolyzation fermentation ethanol industry processed and paper industry.Xylogen is a kind of natural high molecular polymer, by ehter bond and C-C, to be formed by connecting, to have the aromatic polymer compound of three-dimensional structure by phenylpropane monomers such as p-hydroxybenzene propane, guaiacyl propane, cloves base propane, quantitatively being only second to Mierocrystalline cellulose, is the unique non-fossil resource that renewable aryl compound can be provided in a large number of nature.Aromatic compound is the important compound of producing polymkeric substance, medicine intermediate and the fine chemical products such as resin, in people's production practice activity, plays an important role.Therefore the research of, lignin conversion being prepared to aromachemicals receives much attention.
Complex construction and chemically reactive due to xylogen, the research of at present preparing phenols chemical about solid acid catalysis lignin conversion is not also very abundant, patent CN102173980 discloses a kind ofly take silicoaluminate as catalyzer, at high boiling point organic reaction media such as glycerol, in the hydrogen supply dissolvents such as tetraline, catalysis lignin degradation is the method for phenols chemical.Patent US4647704 discloses a kind of Ni-W/SiO
2-Al
2o
3loaded catalyst, take low-carbon (LC) alcohol and water as reaction medium, and temperature of reaction 573～723K, reacts under hydrogen pressure 3.5～24MPa, phenolic compound yield 30%.Patent CN102372607 discloses a kind of in alkaline aqueous solution system, in nitrogen atmosphere, and the method for the single benzene ring phenolic compound of metal nano particle catalysis xylogen hydrogenation degraded preparation.Patent CN101768052 has reported catalyst based with loading type Ni and has had the nitrogenous of formation hydrogen bond ability and/or contain under the effect of oxygen heteroatom small molecule solvent, xylogen hydrocracking generates phenylol, pockwood phenolic group and Syringa oblata Lindl. base aromatics, the method of this patent take in the reaction that water is solvent, and lignin conversion rate is only 25%.Patent CN102964392 discloses a kind of microwave reinforced xylogen in hydrogen supply dissolvent, and mineral acid catalyzed degradation is prepared the method for small molecules phenolic compound.Above method phenolic product yield is generally not high, and because the use of inorganic acid alkali, hydrogen supply dissolvent brings difficulty to the separation of product, has limited catalyst recovery utilization, therefore need to develop the problems and shortcomings that method new in exists to solve it.
Summary of the invention
In order to address the above problem, to the invention provides and a kind ofly take carbon-based solid acid as catalyzer, direct catalysis lignin degradation in aqueous phase system, the method for green production phenols chemical.
The present invention by xylogen, prepare the method for phenols chemical: the xylogen of take is reaction solvent as raw material, carbon-based solid acid as catalyzer, water, by xylogen, carbon-based solid acid and water, be 1:(0.1～0.5 in mass ratio): the ratio of (10～50) is put into autoclave, pass into rare gas element and discharge air in reactor, and make the inert gas pressure in reactor reach 0.5～5MPa, stirring and regulating temperature of reaction is 160 ℃～240 ℃, reaction 0.5～12h; Then reaction solution extracted and purify, obtaining phenols chemical; Wherein said carbon-based solid acid is to take xylogen in the environment of mineral acid, to prepare and obtain as raw material.
Wherein, the described phenols chemical in reaction solution extracts and the method for purifying is preferably, and uses ethyl acetate to extract reaction solution, then reduction vaporization.
Selected catalyst carbon based solid acid in the present invention, its preparation method is as follows: xylogen is added in the mixing solutions of nitric acid and sulfuric acid, under protection of inert gas, stirring reaction 2～24h at 60 ℃～160 ℃, reaction finishes rear standing cooling, after decantation, with hot water, is washed to neutral, after dry milling, obtain described carbon-based solid acid catalyst; Described xylogen and mixed acid solution are 1:(50～200 in mass ratio) configuration.Wherein, described temperature of reaction is preferably 80～100 ℃.Described mixed acid solution consists of: nitric acid massfraction is 5～15%, the massfraction of sulfuric acid is 11～64%, surplus is water.The described xylogen raw material for carbon-based solid acid is alkali lignin, organosolv lignin, enzymolysis xylogen residue or hydrolytic lignin residue; Be preferably enzymolysis xylogen residue, in bio-ethanol technique, the remaining residue that is rich in xylogen after enzymatic hydrolysis and fermentation.
With respect to prior art, the present invention has the following advantages: 1) present method be take water as solvent, and reaction system is simple, and catalyzer and product are easy to separation, and technique environmental protection effectively reduces disposal of pollutants; 2) present method utilizes xylogen as the raw materials of catalyzer, even remaining low activity lignin residue is also applicable to prepare the catalyzer in present method in this reaction, as the catalyzer use of reaction next time, the raw materials of catalyzer of the present invention is simple and easy to get, for being difficult to the lignin residue low alive of reaction, provide new utilizing approach and can realize utilization completely; 3) in present method, the preparation technology of catalyzer is simple with respect to the preparation technology of other sulfonation solid acids, has avoided the use of concentrated nitric acid and the vitriol oil, has reduced equipment corrosion, is easy to sour recycling simultaneously; 4) present method has realized the higher value application of xylogen, reduces the dependence to fossil resources such as oil, turns waste into wealth, and has obvious economic benefit; 5) in method of the present invention, phenols yield can be up to 53%, and the relative selectivity of pockwood phenolic group aromatics product can reach 70%, than prior art, has outstanding advantage.
Embodiment
Method in following embodiment, if no special instructions, is ordinary method.
Embodiment 1:
(1) preparation of carbon-based solid acid: 5g alkali lignin is placed in and 250g mixed acid solution is housed (nitric acid massfraction is 5%; sulfuric acid massfraction is 64%) the three-necked flask with reflux condensate device in; under nitrogen protection and 80 ℃ of oil baths, react 12h; cooling standing; suction filtration after decant; with hot wash, to neutral, till there is no acid ion and detecting, then dry to grind and obtain black carbon based solid acid catalyst.
(2) xylogen is prepared phenols chemical: in stainless steel autoclave, put into 1g alkali lignin, the carbon-based solid acid catalyst that 0.5g utilizes aforesaid method to make, 50ml deionized water, at argon pressure 2MPa, after stirring reaction 12h, cooling standing under 160 ℃ of temperature of reaction, filter and collect unreacting material and catalyzer, and be extracted with ethyl acetate reaction solution, after extraction liquid rotary evaporation, obtain phenols chemical.Phenolic product comes quantitative and qualitative analysis to detect with gas-chromatography coupling mass spectrograph, and product relative selectivity is defined as the relative peak area of product on color atlas.
After reaction finishes, recording lignin conversion rate is 52%, phenolic product yield 35%, and pockwood phenolic group aromatics product relative selectivity is 62%.
Embodiment 2:
(1) preparation of carbon-based solid acid: 5g alkali lignin is placed in and 1000g mixed acid solution is housed (nitric acid massfraction is 15%; sulfuric acid massfraction is 47%) the three-necked flask with reflux condensate device in; under nitrogen protection and 160 ℃ of oil baths, react 4h; cooling standing; suction filtration after decant; with hot wash, to neutral, till there is no acid ion and detecting, then dry to grind and obtain black carbon based solid acid catalyst.
(2) xylogen is prepared phenols chemical: in stainless steel autoclave, put into 1g organosolv lignin, the carbon-based solid acid catalyst that 0.1g utilizes aforesaid method to make, 10ml deionized water, at helium pressure 5MPa, after stirring reaction 0.5h, cooling standing under 240 ℃ of temperature of reaction, filter and collect unreacting material and catalyzer, and be extracted with ethyl acetate reaction solution, after extraction liquid rotary evaporation, obtain phenols chemical.Phenolic product comes quantitative and qualitative analysis to detect with gas-chromatography coupling mass spectrograph, and product relative selectivity is defined as the relative peak area of product on color atlas.
After reaction finishes, recording lignin conversion rate is 32%, phenolic product yield 21%, and pockwood phenolic group aromatics product relative selectivity is 57%.
Embodiment 3:
(1) preparation of carbon-based solid acid: 5g hydrolytic lignin is placed in and 500g mixed acid solution is housed (nitric acid massfraction is 15%; sulfuric acid massfraction is 64%) the three-necked flask with reflux condensate device in; under argon shield and 60 ℃ of oil baths, react 8h; cooling standing; suction filtration after decant; with hot wash, to neutral, till there is no acid ion and detecting, then dry to grind and obtain black carbon based solid acid catalyst.
(2) xylogen is prepared phenols chemical: in stainless steel autoclave, put into 1g hydrolytic lignin, the carbon-based solid acid catalyst that 0.4g utilizes aforesaid method to make, 20ml deionized water, at nitrogen pressure 4MPa, after stirring reaction 2h, cooling standing under 220 ℃ of temperature of reaction, filter and collect unreacting material and catalyzer, and be extracted with ethyl acetate reaction solution, after extraction liquid rotary evaporation, obtain phenols chemical.Phenolic product comes quantitative and qualitative analysis to detect with gas-chromatography coupling mass spectrograph, and product relative selectivity is defined as the relative peak area of product on color atlas.
After reaction finishes, recording lignin conversion rate is 57%, phenolic product yield 40%, and pockwood phenolic group aromatics product relative selectivity is 57%.
Embodiment 4:
(1) preparation of carbon-based solid acid: 5g enzymolysis xylogen is placed in and 500g mixed acid solution is housed (nitric acid massfraction is 10%; sulfuric acid massfraction is 47%) the three-necked flask with reflux condensate device in; under argon shield and 100 ℃ of oil baths, react 8h; cooling standing; suction filtration after decant; with hot wash, to neutral, till there is no acid ion and detecting, then dry to grind and obtain black carbon based solid acid catalyst.
(2) xylogen is prepared phenols chemical: in stainless steel autoclave, put into 1g enzymolysis xylogen, the carbon-based solid acid catalyst that 0.4g utilizes aforesaid method to make, 20ml deionized water, at nitrogen pressure 5MPa, after stirring reaction 4h, cooling standing under 200 ℃ of temperature of reaction, filter and collect unreacting material and catalyzer, and be extracted with ethyl acetate reaction solution, after extraction liquid rotary evaporation, obtain phenols chemical.Phenolic product comes quantitative and qualitative analysis to detect with gas-chromatography coupling mass spectrograph, and product relative selectivity is defined as the relative peak area of product on color atlas.
After reaction finishes, recording lignin conversion rate is 57%, phenolic product yield 41%, and pockwood phenolic group aromatics product relative selectivity is 61%.
Embodiment 5:
(1) preparation of carbon-based solid acid: 5g enzymolysis xylogen is placed in and 500g mixed acid solution is housed (nitric acid massfraction is 5%; sulfuric acid massfraction is 47%) the three-necked flask with reflux condensate device in; under nitrogen protection and 100 ℃ of oil baths, react 8h; cooling standing; suction filtration after decant; with hot wash, to neutral, till there is no acid ion and detecting, then dry to grind and obtain black carbon based solid acid catalyst.
(2) xylogen is prepared phenols chemical: in stainless steel autoclave, put into 1g enzymolysis xylogen, the carbon-based solid acid catalyst that 0.4g utilizes aforesaid method to make, 20ml deionized water, at nitrogen pressure 4MPa, after stirring reaction 2h, cooling standing under 220 ℃ of temperature of reaction, filter and collect unreacting material and catalyzer, and be extracted with ethyl acetate reaction solution, after extraction liquid rotary evaporation, obtain phenols chemical.Phenolic product comes quantitative and qualitative analysis to detect with gas-chromatography coupling mass spectrograph, and product relative selectivity is defined as the relative peak area of product on color atlas.
After reaction finishes, recording lignin conversion rate is 67%, phenolic product yield 53%, and pockwood phenolic group aromatics product relative selectivity is 70%.
Embodiment 6:
(1) preparation of carbon-based solid acid: 5g enzymolysis xylogen is placed in and 250g mixed acid solution is housed (nitric acid massfraction is 5%; sulfuric acid massfraction is 33%) the three-necked flask with reflux condensate device in; under nitrogen protection and 120 ℃ of oil baths, react 4h; cooling standing; suction filtration after decant; with hot wash, to neutral, till there is no acid ion and detecting, then dry to grind and obtain black carbon based solid acid catalyst.
(2) xylogen is prepared phenols chemical: in stainless steel autoclave, put into 1g organosolv lignin, the carbon-based solid acid catalyst that 0.2g utilizes aforesaid method to make, 40ml deionized water, at nitrogen pressure 0.5MPa, after stirring reaction 8h, cooling standing under 160 ℃ of temperature of reaction, filter and collect unreacting material and catalyzer, and be extracted with ethyl acetate reaction solution, after extraction liquid rotary evaporation, obtain phenols chemical.Phenolic product comes quantitative and qualitative analysis to detect with gas-chromatography coupling mass spectrograph, and product relative selectivity is defined as the relative peak area of product on color atlas.
After reaction finishes, recording lignin conversion rate is 53%, phenolic product yield 37%, and pockwood phenolic group aromatics product relative selectivity is 66%.
Embodiment 7:
(1) preparation of carbon-based solid acid: 5g enzymolysis xylogen is placed in and 500g mixed acid solution is housed (nitric acid massfraction is 5%; sulfuric acid massfraction is 11%) the three-necked flask with reflux condensate device in; under nitrogen protection and 100 ℃ of oil baths, react 8h; cooling standing; suction filtration after decant; with hot wash, to neutral, till there is no acid ion and detecting, then dry to grind and obtain black carbon based solid acid catalyst.
(2) xylogen is prepared phenols chemical: in stainless steel autoclave, put into 1g enzymolysis xylogen, the carbon-based solid acid catalyst that 0.4g utilizes aforesaid method to make, 20ml deionized water, at nitrogen pressure 2MPa, after stirring reaction 0.5h, cooling standing under 240 ℃ of temperature of reaction, filter and collect unreacting material and catalyzer, and be extracted with ethyl acetate reaction solution, after extraction liquid rotary evaporation, obtain phenols chemical.Phenolic product comes quantitative and qualitative analysis to detect with gas-chromatography coupling mass spectrograph, and product relative selectivity is defined as the relative peak area of product on color atlas.
After reaction finishes, recording lignin conversion rate is 21%, phenolic product yield 10%, and pockwood phenolic group aromatics product relative selectivity is 61%.
Embodiment 8:
(1) preparation of carbon-based solid acid: 5g enzymolysis xylogen is placed in and 500g mixed acid solution is housed (nitric acid massfraction is 5%; sulfuric acid massfraction is 64%) the three-necked flask with reflux condensate device in; under nitrogen protection and 100 ℃ of oil baths, react 8h; cooling standing; suction filtration after decant; with hot wash, to neutral, till there is no acid ion and detecting, then dry to grind and obtain black carbon based solid acid catalyst.
(2) xylogen is prepared phenols chemical: in stainless steel autoclave, put into 1g enzymolysis xylogen, the carbon-based solid acid catalyst that 0.4g utilizes aforesaid method to make, 20ml deionized water, at nitrogen pressure 2MPa, after stirring reaction 4h, cooling standing under 220 ℃ of temperature of reaction, filter and collect unreacting material and catalyzer, and be extracted with ethyl acetate reaction solution, after extraction liquid rotary evaporation, obtain phenols chemical.Phenolic product comes quantitative and qualitative analysis to detect with gas-chromatography coupling mass spectrograph, and product relative selectivity is defined as the relative peak area of product on color atlas.
After reaction finishes, recording lignin conversion rate is 77%, phenolic product yield 50%, and pockwood phenolic group aromatics product relative selectivity is 68%.
Claims (5)
1. a carbon-based solid acid catalysis lignin degradation is prepared the method for phenols chemical, it is characterized in that: the xylogen of take is reaction solvent as raw material, carbon-based solid acid as catalyzer, water, by xylogen, carbon-based solid acid and water, be 1:(0.1～0.5 in mass ratio): the ratio of (10～50) is put into autoclave, pass into rare gas element and discharge air in reactor, and make the inert gas pressure in reactor reach 0.5～5MPa, stirring and regulating temperature of reaction is 160 ℃～240 ℃, reaction 0.5～12h; Then reaction solution extracted and purify, obtaining phenols chemical; Wherein said carbon-based solid acid is to take xylogen in the environment of mineral acid, to prepare and obtain as raw material.
2. method according to claim 1, it is characterized in that, the preparation method of described carbon-based solid acid is as follows: xylogen is added in the mixing solutions of nitric acid and sulfuric acid, under protection of inert gas, stirring reaction 2～24h at 60 ℃～160 ℃, reaction finishes rear standing cooling, after decantation, with hot water, washed to neutral, after dry milling, obtained described carbon-based solid acid catalyst; Described xylogen and mixed acid solution are 1:(50～200 in mass ratio) configuration.
3. method according to claim 2, is characterized in that, described oil bath temperature is 80～100 ℃.
4. method according to claim 2, is characterized in that, described mixed acid solution consists of: the massfraction of nitric acid is 5～15%, the massfraction of sulfuric acid is 11～64%, surplus is water.
5. method according to claim 1 and 2, is characterized in that, the described xylogen raw material for carbon-based solid acid is alkali lignin, organosolv lignin, enzymolysis xylogen residue or hydrolytic lignin residue.
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Cited By (3)
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| CN106345491A (en) * | 2016-07-29 | 2017-01-25 | 中国科学院广州能源研究所 | Grafted solid acid catalyst, preparation method thereof and application of grafted solid acid catalyst in saccharification process of lignocellulose |
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