CN103360192B - Method for preparing monoaromatic compound through carrying out microwave synergistic catalyzed oxidative degradation on alkali lignin - Google Patents
Method for preparing monoaromatic compound through carrying out microwave synergistic catalyzed oxidative degradation on alkali lignin Download PDFInfo
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Abstract
The invention discloses a method for preparing a monoaromatic compound through carrying out microwave synergistic catalyzed oxidative degradation on alkali lignin. The method comprises the following steps of: adding 100 parts by weight of alkali lignin and 660 parts by weight of water into a microwave reaction tank, adding 26-130 parts by weight of NaOH, uniformly stirring the mixture, then, adding 3.3-33 parts by weight of CuO, 0.33-3.3 parts of Fe2(SO4)3 and 27-1055 parts by weight of oxidizing agent, setting microwave reaction power at 300-600W and the microwave frequency at 2450MHz+/-15Hz, and carrying out degradation reaction at the temperature of 160-190 DEG C for 10-90min; and cooling, filtering, adjusting the pH value of a filtrate to 3-6 by using 1-2M of H2SO4, centrifuging and removing insoluble substances to obtain a solution containing the monoaromatic compound. The method has the characteristics of low reaction temperature, environment friendliness because of the adoption of waterborne reaction conditions, difficulty in coking and high yield of the monoaromatic compound.
Description
Technical field
The present invention relates to single benzene ring type compounds, particularly relate to a kind of method that microwave cooperating catalyzing oxidizing degrading alkali lignin prepares single benzene ring type compounds.
Background technology
Xylogen is one of main component of plant skeleton, be also content maximum containing aromatic series natural polymers, account for 15% ~ 30% of plant weight, 40% of energy.In paper-making pulping industry, the industrial lignin of about 5,000 ten thousand tons can be produced every year, sulfonated lignin in industrial lignin and alkali lignin derive from acid polishing and alkaline process technique respectively, and sulfonated lignin are recovered industrial uses such as being widely used in Surfactants Used for Oil field, cement water reducing agent, agrochemicals, industry adhesive because having certain surfactivity; And the alkali lignin accounting for industrial lignin 90% is not owing to possessing surfactivity, direct application performance is poor, usually xylogen is burnt to reclaim the alkali in black liquor of pulp making by alkali reclaiming method for large-scale slurrying enterprise, the method investment cost is high, biomass resource is burnt, and is a kind of Land use systems of low value.And alkali lignin is reclaimed carry out chemical modification and prepare macromolecular compound or carry out degrading that to obtain low molecular compound be two main paties of alkali lignin high-value-use to alkali lignin.
Because the reactive behavior of alkali lignin is poor, early stage degraded is all carry out under High Temperature High Pressure, special catalyzer or system.Patent documentation CN101234958 discloses a kind of method that alkali lignin prepares vanillin food grade,1000.000000ine mesh, at CO
2, He, N
2deng in inert gas atmosphere, under the temperature of reaction of 300 ~ 800 DEG C, with metals such as Pd, Cu, Ag for catalyzer, alkali lignin is degraded at pyrocrack furnace, the vanillin food grade,1000.000000ine mesh of purity more than 70% can be obtained, but there are no transformation efficiency with optionally report.American documentation literature US5807952 discloses xylogen under NaOH exists, and at 400 ~ 600 DEG C of temperature, be degraded to micromolecule phenolic, the transformation efficiency of xylogen is 15 ~ 60%.Dellinger by xylogen at N
2gas and O
2gas mass ratio is in the mixed gas of 96:4, carry out 200 ~ 900 DEG C of high temperature oxidation degradeds, degraded product mainly comprises syringol, guaiacyl, phenol and other fortified phenol, aldehydes matter accounts for the 40wt% detecting product, but concrete yield (Environmental Science & Technology is not provided, 2012,46:12994-13001).American documentation literature US4647704 discloses a kind of with SiO
2/ Al
2o
3load Ni-W catalyzer is at low-carbon (LC) alcohol and water as reaction medium, and temperature of reaction is 300 ~ 450 DEG C, and H2 gas dividing potential drop is 3.5 ~ 24MPa, and the yield of phenolic compound is 30%.Chinese invention patent document CN102372607A discloses a kind of method preparing single benzene ring compound from alkali lignin, temperature of reaction 90 ~ 180 DEG C, hydrogen pressure is preferably 1.0 ~ 10.0MPa, under the effect of the catalyst with metal nanoparticles such as Au, Ru, Ni, reaction times is 10h, hydrogenation degraded alkali lignin prepares single benzene ring phenolic compound, and the yield calculating its single benzene ring phenolic compound is up to 45%.As can be seen here, the heat of the xylogen of prior art or oxidative degradation are carried out in High Temperature High Pressure usually, and single benzene ring type compounds yield is not high, carries out hydrogenation degraded, although yield is high, DeR pressure must be caused greatly to increase, and degraded cost increases greatly.
The report that microwave introduces chemical reaction is a lot, due to the molecular motion in micro-wave energy greatly shortening heat conduction time, aggravation system, the activation energy that improves molecule average energy, reduce reaction, microwave starts to be applied to the biomass chemical reaction of difficult degradation to improve chemical reaction velocity and selectivity of chemical equation in recent years.Ani reports at N
2in gas, under the gac of 25wt% exists, use the microwave thermal degraded 25min of 300 ~ 450W power, temperature of reaction system reaches 500 DEG C, oil palm shell is prepared into bio oil, wherein in bio oil, the yield of low molecule aldehydes matter is 4.8%(Journal of Analytical and AppliedPyrolysis, 2012,96:162-172).Patent CN102924204A discloses microwave reinforced xylogen in ionic liquid 1-ethyl-3-methylimidazole medium, degrade under 140 ~ 200 DEG C of microwave actions 20 ~ 60min, the yield of micromolecule phenolic is 8.3 ~ 30.8%, but the cost of ionic liquid is high, also has longer distance from industrialization.Gu reports and utilizes the SBA-15 of lanthanum modification as catalyzer, at H
2o
2in oxidation system, microwave degradation is single phenolic compound.At microwave power 200W, the highest molar yield of the small molecules list phenolic compound that degraded 10min obtains is 31.48%, amounts to into mass yield and is about 2.7%(Maderas.Ciencia y tecnolog í a, 2012,14:31-42).
Introduce microwave assistant degradation xylogen, reduce temperature of reaction to a great extent, shorten the degradation time of xylogen, make its reaction conditions gentle, energy consumption is low, if but there is no suitable catalyzer, the yield that alkali lignin is degraded to single benzene ring type compounds in water-based reaction system would be still lower.
Summary of the invention
The present invention is directed to above problem, provide a kind of in water-based system microwave cooperating degraded alkali lignin prepare the method that single benzene ring type compounds yield is greater than 10%.
The present invention, under alkaline aqueous solution system, under microwave cooperating effect, selects suitable CuO and Fe
2(SO
4)
3for catalyzer, with H
2o
2or Na
2s
2o
8for oxygenant, improve the degradation rate of xylogen and the yield of single benzene ring type compounds.
Object of the present invention is achieved through the following technical solutions:
Microwave cooperating catalyzing oxidizing degrading alkali lignin prepares the method for single benzene ring type compounds; Comprise the following steps:
1) water of 100 weight part alkali lignins and 660 weight parts is joined in microwave reaction tank, add the NaOH of 26 ~ 130 weight parts, stir, then add the CuO of 3.3 ~ 33 weight parts, the Fe of 0.33 ~ 3.3 weight part
2(SO
4)
3with the oxygenant of 27 ~ 1055 weight parts, the power arranging microwave reactor is 300 ~ 600W, and microwave frequency is 2450MHz ± 15Hz, at 160 ~ 190 DEG C, carry out DeR 10 ~ 90min; Described oxygenant is H
2o
2or Na
2s
2o
8;
2) reaction terminates rear cooling, filters, adds H in filtrate
2sO
4solution adjust ph to 3 ~ 6, centrifugal removing insolubles, obtains the solution containing single benzene ring type compounds.
Preferably, step 1) in alkali lignin be alkali paper-making pulping waste liquor reclaim Wheat Straw Lignin from Alkali Pulping, bamboo alkali lignin, wood pulp alkali xylogen, bagasse alkali-lignin or sahio base xylogen.Described H
2sO
4the concentration of solution is 1 ~ 2M.Described H
2o
2mass concentration be 30wt%.Described CuO and Fe
2(SO
4)
3mass ratio be 10:1.The yield of described single benzene ring compound is greater than 10%, and the degradation rate of alkali lignin is greater than 90%.
The prominent feature of the technology of the present invention utilizes microwave cooperating, reduces temperature of reaction and reaction times, solves lignin degradation and prepare long reaction time in single phenyl ring class process, and temperature is high and easily produce the problem of biomass coking, under microwave cooperating effect, with H
2o
2or Na
2s
2o
8in water-based system, obtain the degradation rate of high alkali lignin as oxygenant and select suitable CuO and Fe
2(SO
4)
3for catalyzer, improve the yield of single benzene ring type compounds of xylogen.
The present invention compared with prior art has following outstanding advantages and effect:
1, the technology of the present invention introduces the degraded of microwave cooperating xylogen, and the reaction times is short, and efficiency is high, and compared with conventional high-temperature high pressure degradation technique, without the need to using high-tension apparatus, process is easy to the advantage that controls, cost is low;
2, the present invention's reaction is with H in water-based system
2o
2or Na
2s
2o
8for oxygenant, CuO and Fe
2(SO
4)
3for catalyzer, without the need to an organic solvent, catalyzer recycling capable of circulation, substantially increases the degradation rate of alkali lignin and the yield of single benzene ring type compounds simultaneously, has economy and environmental protection double effect.
Accompanying drawing explanation
The liquid chromatogram containing single benzene ring type compounds solution of Fig. 1 for obtaining after the alkali lignin degraded described in embodiment 1.
Fig. 2 is the liquid chromatogram containing the standard substance of single benzene ring compound in degraded product.
Embodiment
Measure single benzene ring type compounds yield with efficient liquid phase chromatographic analysis in the present invention, analysis condition is as follows:
Adopt Prominence LC-20A type Shimadzu high performance liquid chromatograph, Agilent SB-C18 post, column temperature 40 DEG C, detector is UV-detector, determined wavelength 280nm, adopt ternary geopressure gradient elution process to carry out separation detection to product, mobile phase A is the phosphate aqueous solution of pH=2.0, B is methyl alcohol, and C is acetonitrile.Gradient elution program is 0 ~ 40min:V
a: V
b: V
c=100:0:0; 40 ~ 45min:V
a: V
b: V
c=65.8:17.1:17.1; 45 ~ 46min:V
a: V
b: V
c=40:30:30; 46 ~ 48min:V
a: V
b: V
c=0:0:100; After 48min: V
a: V
b: V
c=100:0:0.
Liquid chromatography-mass spectrometry is carried out to degraded product, determine the molecular weight of recognizate respectively, the title of single benzene ring substance in degraded product is tentatively determined according to molecular weight, then, choose the retention time going out peak in the liquid chromatography of corresponding standard substance under same analysis condition, the concrete title of single benzene ring type compounds after checking degraded.
The degradation rate of alkali lignin and the yield of single benzene ring type compounds are respectively by formulae discovery below:
Solid masses after the add-on of the degradation rate %=(xylogen of alkali lignin-reacted acid out) add-on × 100% of/alkali lignin
Add-on × 100% of the yield sum/alkali lignin of each single benzene ring type compounds of yield %=of single benzene ring type compounds.
Embodiment 1
The water getting 100g sahio base xylogen and 660g joins in microwave reaction tank, adds the NaOH of 26g, makes it dissolve, then adds the CuO of 33g, the Fe of 3.3g
2(SO
4)
3with the H of 1000g
2o
2, the power arranging microwave reactor is 300W, and microwave frequency is 2450MHz; Degrade 60min at 180 DEG C; Reaction terminates rear cooling, Filtration of catalyst; Add the H of 1M
2sO
4, regulator solution pH value to 6, centrifugal removing insolubles, obtains containing single benzene ring type compounds solution.
Fig. 1 is the liquid chromatogram obtaining product after embodiment 1 is degraded, by the contrast (Fig. 2) of the standard liquid chromatograph figure with single benzene ring type compounds, determine that in the degraded product of embodiment 1, single benzene ring type compounds is respectively: gallic acid, P-hydroxybenzoic acid, p-Hydroxybenzaldehyde, vanillic acid, syringic acid, Vanillin, P-coumaric acid, forulic acid, sinapinic acid, isoferulic acid and syringic aldehyde.
According to reversed-phase liquid chromatography separation principle, the unknown peak that leading portion occurs in color atlas 1 should be the less degraded product being greater than 2 containing the polymerization degree of phenyl ring of polarity, and occur after 42min should be the stronger small molecules aliphatic chain organic acid substance of polarity.
Table 1 is the molecular weight of the material detected according to degraded product liquid phase-mass spectrometry, and the standard substance of the related substances determined is through residence time that liquid chromatography is determined and concentration and the typical curve equation going out peak area.
Table 1
Note: Y is the concentration of single benzene ring type compounds, and X is that single benzene ring type compounds goes out peak area in liquid chromatography
Table 2 is after embodiment 1 is degraded, and according to the relation (see table 1) going out peak area and concentration of liquid chromatography, calculates the yield of the various single benzene ring type compounds obtained.
The yield of various single benzene ring type compounds is obtained after the degraded of table 2 alkali lignin
Below embodiment about containing single benzene ring type compounds determination and obtain various single benzene ring type compounds yield defining method with embodiment 1, do not provide one by one.
Embodiment 2
The water getting 100g Wheat Straw Lignin from Alkali Pulping and 660g joins in microwave reaction tank, adds the NaOH of 80g, makes it dissolve, then adds the CuO of 3.3g, the Fe of 0.33g
2(SO
4)
3be the H of 30% with the mass concentration of 495g
2o
2, the power arranging microwave reactor is 300W, and microwave frequency is 2450MHz; Degrade 30min at 180 DEG C; Reaction terminates rear cooling, Filtration of catalyst; Add the H of 2M
2sO
4, regulator solution pH value to 3, centrifugal removing insolubles, obtains containing single benzene ring type compounds solution.
Embodiment 3
The water getting 100g wood pulp alkali xylogen and 660g joins in microwave reaction tank, adds the NaOH of 106g, makes it dissolve, then adds the CuO of 7g, the Fe of 0.7g
2(SO
4)
3be the H of 30% with the mass concentration of 600g
2o
2, the power arranging microwave reactor is 300W, and microwave frequency is 2450MHz; Degrade 20min at 170 DEG C; Reaction terminates rear cooling, Filtration of catalyst; Add the H of 2M
2sO
4, regulator solution pH value to 4, centrifugal removing insolubles, obtains containing single benzene ring type compounds solution.
Embodiment 4
The water getting 100g bagasse alkali-lignin and 660g joins in microwave reaction tank, adds the NaOH of 130g, makes it dissolve, then adds the CuO of 13g, the Fe of 1.3g
2(SO
4)
3with the H of 850g
2o
2, the power arranging microwave reactor is 300W, and microwave frequency is 2450MHz; Degrade 40min at 160 DEG C; Reaction terminates rear cooling, Filtration of catalyst; Add the H of 2M
2sO
4, regulator solution pH value to 6, centrifugal removing insolubles, obtains containing single benzene ring type compounds solution.
Embodiment 5
The water getting 100g bamboo alkali lignin and 660g joins in microwave reaction tank, adds the NaOH of 50g, makes it dissolve, then adds the CuO of 20g, the Fe of 2.0g
2(SO
4)
3with the H of 1055g
2o
2, the power arranging microwave reactor is 300W, and microwave frequency is 2450MHz; Degrade 40min at 180 DEG C; Reaction terminates rear cooling, Filtration of catalyst; Add the H of 2M
2sO
4, regulator solution pH value to 6, centrifugal removing insolubles, obtains containing single benzene ring type compounds solution.
Embodiment 6
The water getting 100g Wheat Straw Lignin from Alkali Pulping and 660g joins in microwave reaction tank, adds the NaOH of 78g, makes it dissolve, then adds the CuO of 3.3g, the Fe of 0.33g
2(SO
4)
3with the H of 1055g
2o
2, the power arranging microwave reactor is 300W, and microwave frequency is 2450MHz; Degrade 10min at 190 DEG C; Reaction terminates rear cooling, Filtration of catalyst; Add the H of 2M
2sO
4, regulator solution pH value to 6, centrifugal removing insolubles, obtains containing single benzene ring type compounds solution.
Embodiment 7
The water getting 100g Wheat Straw Lignin from Alkali Pulping and 660g joins in microwave reaction tank, adds the NaOH of 78g, stirs, and makes it dissolve, then adds the CuO of 13g, the Fe of 1.3g
2(SO
4)
3with the Na of 27g
2s
2o
8, the power arranging microwave reactor is 300W, and microwave frequency is 2450MHz; Degrade 90min at 180 DEG C; After reaction terminates, cooling, Filtration of catalyst; Add the H of 2M
2sO
4, regulator solution pH value to 6, centrifugal removing insolubles, obtains containing single benzene ring type compounds solution.
Comparative example 1
The water getting 100g sahio base xylogen and 660g joins in microwave reaction tank, adds the NaOH of 78g, stirs, and makes it dissolve, then adds the H of 1000g
2o
2, the power arranging microwave reactor is 300W, and microwave frequency is 2450MHz; Degrade 60min at 180 DEG C; Reaction terminates rear cooling, adds the H of 2M
2sO
4, regulator solution pH value to 6, centrifugal removing insolubles, obtains containing single benzene ring type compounds solution.
Comparative example 2
The water getting 100g sahio base xylogen and 660g joins in microwave reaction tank, adds the NaOH of 78g, stirs, and makes it dissolve, then adds the CuO of 13g, and the power arranging microwave reactor is 300W, and microwave frequency is 2450MHz; Degrade 60min at 180 DEG C; Reaction terminates rear cooling, filters, removing catalyzer; The H of 2M is added in filtrate
2sO
4, regulator solution pH value to 6, centrifugal removing insolubles, obtains containing single benzene ring type compounds solution.
Comparative example 3
The water getting 100g sahio base xylogen and 660g joins in microwave reaction tank, adds the NaOH of 78g, stirs, and makes it dissolve, then adds the CuO of 13g, the Fe of 1.3g
2(SO
4)
3, the power arranging microwave reactor is 300W, and microwave frequency is 2450MHz; Degrade 60min at 180 DEG C; Reaction terminates rear cooling, filters, removing catalyzer; The H of 2M is added in filtrate
2sO
4, regulator solution pH value to 6, centrifugal removing insolubles, obtains containing single benzene ring type compounds solution.
Implementation result explanation
The yield of table 3 single benzene ring type compounds for the embodiment of the present invention obtains and the test data of alkali lignin degradation rate.
The contrast of the data of table 3 alkali lignin degradation rate and single benzene ring compound yield
In order to implementation result of the present invention is described, by embodiment and under microwave cooperating separately oxidation or separately the yield of single benzene ring type compounds that obtains of catalyzed degradation alkali lignin and alkali lignin degradation rate contrast, contrast effect is in table 3.
As can be seen from Table 3, under reaction system of the present invention (embodiment 1 ~ 7), the degradation rate of alkali lignin all can reach more than 90%, and the yield of single benzene ring type compounds all reaches more than 10%; And when not using catalyzer of the present invention in DeR system, independent hydrogen peroxide effect, although the degradation rate of alkali lignin can reach 85.57%, the yield of single benzene ring type compounds is only 2.52%(comparative example 1); When reaction system does not use oxygenant, only add a kind of catalyzer or add two kinds of catalyzer, the degradation rate of alkali lignin is all lower than 50%, the yield of single benzene ring type compounds is all lower than 4%(comparative example 2 ~ 3), all be far smaller than the result that the inventive method obtains, visible the present invention prepares single benzene ring type compounds at degraded alkali lignin and has significant effect, is that prior art is incomparable.
Claims (5)
1. microwave cooperating catalyzing oxidizing degrading alkali lignin prepares the method for single benzene ring type compounds, it is characterized in that comprising the following steps:
1) water of 100 weight part alkali lignins and 660 weight parts is joined in microwave reaction tank, add the NaOH of 26 ~ 130 weight parts, stir, then add the CuO of 3.3 ~ 33 weight parts, the Fe of 0.33 ~ 3.3 weight part
2(SO
4)
3with the oxygenant of 27 ~ 1055 weight parts, the power arranging microwave reactor is 300 ~ 600W, and microwave frequency is 2450MHz ± 15Hz, at 160 ~ 190 DEG C, carry out DeR 10 ~ 90min; Described oxygenant is H
2o
2or Na
2s
2o
8;
2) reaction terminates rear cooling, filters, adds H in filtrate
2sO
4solution adjust ph to 3 ~ 6, centrifugal removing insolubles, obtains the solution containing single benzene ring type compounds; The yield of described single benzene ring compound is greater than 10%, and the degradation rate of alkali lignin is greater than 90%.
2. method according to claim 1, is characterized in that: step 1) in alkali lignin be alkali paper-making pulping waste liquor reclaim Wheat Straw Lignin from Alkali Pulping, bamboo alkali lignin, wood pulp alkali xylogen, bagasse alkali-lignin or sahio base xylogen.
3. method according to claim 1, is characterized in that: described H
2sO
4the concentration of solution is 1 ~ 2M.
4. method according to claim 1, is characterized in that: described H
2o
2mass concentration be 30wt%.
5. method according to claim 1, is characterized in that: described CuO and Fe
2(SO
4)
3mass ratio be 10:1.
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| CN103626642A (en) * | 2013-11-28 | 2014-03-12 | 上海应用技术学院 | Method for preparing vanillin |
| CN104910341B (en) * | 2015-06-24 | 2017-07-11 | 湖南师范大学 | Method for preparing lignin phenolic resin adhesive by treating papermaking waste liquid with microwave-CuO |
| CN106881113B (en) * | 2015-12-16 | 2019-03-01 | 中国石油化工股份有限公司 | A kind of biomass carbon sulfonic acid and preparation method thereof and method with its catalytic esterification synthesizing adipic acid dibutyl ester |
| CN106946660B (en) * | 2017-02-07 | 2020-05-22 | 广西科学院 | Method for preparing monophenol compound by catalyzing lignin degradation through ammonia complex |
| CN106957211A (en) * | 2017-04-18 | 2017-07-18 | 中国科学技术大学 | A kind of method of catalytic degradation lignin |
| CN109824497B (en) * | 2019-03-06 | 2020-10-27 | 华南理工大学 | Method for preparing single benzene ring compound by degrading alkali lignin through microwave synergistic metalloporphyrin catalytic oxidation |
| CN110078877B (en) * | 2019-04-26 | 2021-07-27 | 福州大学 | Method for preparing dispersant by using lignin degradation product and application |
| CN110257097B (en) * | 2019-07-15 | 2022-02-11 | 中国林业科学研究院林产化学工业研究所 | Method for preparing bio-oil by microwave-assisted lignin hydrogenolysis |
| CN111484405B (en) * | 2020-04-26 | 2023-03-31 | 苏州纳创佳环保科技工程有限公司 | Method for preparing aromatic acid monomer by comprehensively utilizing agricultural waste raw materials |
| CN111495329B (en) * | 2020-04-26 | 2023-04-28 | 苏州铭泽新材料科技有限公司 | Method for synthesizing porous metal organic framework based on lignin degradation products |
| CN113512075A (en) * | 2021-03-05 | 2021-10-19 | 复旦大学 | Method for preparing aromatic chemicals by microwave-assisted hydrothermal liquefaction of lignin |
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