CN103360192A - 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 the method that a kind of microwave cooperating catalyzing oxidizing degrading alkali lignin prepares single benzene ring type compounds.
Background technology
Xylogen is one of main component of plant skeleton, also be the content maximum contain the aromatic series natural polymers, account for 15%～30% of plant weight, 40% of energy.In the paper-making pulping industry, the annual industrial lignin that can produce about 5,000 ten thousand tons, sulfonated lignin in the industrial lignin and alkali lignin derive from respectively acid polishing and alkaline process technique, 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 account for the alkali lignin of industrial lignin 90% owing to do not possess surfactivity, directly application performance is poor, usually burn xylogen to reclaim the alkali in the 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 mode of utilizing of low value.Carry out that chemical modification prepares macromolecular compound or alkali lignin to be degraded to obtain low molecular compound be two main paties of alkali lignin high-value-use and alkali lignin reclaimed.
Because the reactive behavior of alkali lignin is relatively poor, early stage degraded all is to carry out under High Temperature High Pressure, special catalyzer or system.Patent documentation CN101234958 discloses the method that a kind of alkali lignin prepares vanillin food grade,1000.000000ine mesh, at CO
2, He, N
2In inert gas atmosphere, under 300～800 ℃ temperature of reaction, take metals such as Pd, Cu, Ag as catalyzer, alkali lignin is degraded at pyrocrack furnace, can obtain purity and surpass 70% vanillin food grade,1000.000000ine mesh, but there are no transformation efficiency with optionally report.American documentation literature US5807952 discloses xylogen in the presence of NaOH, is the small molecules phenolic compound 400～600 ℃ of drop in temperature solutions, and the transformation efficiency of xylogen is 15～60%.Dellinger with xylogen at N
2Gas and O
2The gas mass ratio is in the mixed gas of 96:4, carry out 200～900 ℃ of high temperature oxidation degradeds, degraded product mainly comprises syringol, guaiacyl, phenol and other fortified phenol, aldehydes matter accounts for the 40wt% that detects product, but concrete yield (Environmental Science ﹠amp is not provided; Technology, 2012,46:12994-13001).American documentation literature US4647704 discloses a kind of with SiO
2/ Al
2O
3As reaction medium, temperature of reaction is 300～450 ℃ to load Ni-W catalyzer at the low-carbon (LC) alcohol and water, 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 for preparing single benzene ring compound from alkali lignin, 90～180 ℃ of temperature of reaction, 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 that calculates its single benzene ring phenolic compound is up to 45%.This shows that the heat of the xylogen of prior art or oxidative degradation are carried out in High Temperature High Pressure usually, single benzene ring type compounds yield is not high, carries out the hydrogenation degraded, although the yield height, must cause DeR pressure greatly to increase, the degraded cost increases greatly.
The report that microwave is introduced chemical reaction is a lot, owing to the greatly molecular motion in shortening heat conduction time, the aggravation system of micro-wave energy, improve the molecule average energy, reduce the activation energy of reaction, microwave begins 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 has reported at N
2In the gas, the gac of 25wt% exists lower, use the microwave thermal degraded 25min of 300～450W power, temperature of reaction system reaches 500 ℃, the oil palm shell is prepared into bio oil, wherein the yield of low molecular phenolics material is 4.8%(Journal of Analytical and Applied Pyrolysis in the bio oil, 2012,96:162-172).Patent CN102924204A discloses microwave reinforced xylogen in ionic liquid 1-ethyl-3-methylimidazole medium, 20～60min degrades under 140～200 ℃ of microwave actions, the yield of small molecules phenolic compound is 8.3～30.8%, but the cost of ionic liquid is high, also has long distance from industrialization.Gu has reported that the SBA-15 that utilizes the lanthanum modification is as catalyzer, at H
2O
2Microwave degradation is single phenolic compound in the oxidation system.At microwave power 200W, the highest molar yield of the small molecules list phenolic compound that degraded 10min obtains is 31.48%, amount to into mass yield and be about 2.7%(Maderas.Ciencia y tecnolog í a, and 2012,14:31-42).
Introduce the microwave assistant degradation xylogen, reduced to a great extent temperature of reaction, shortened the degradation time of xylogen, make its reaction conditions gentle, energy consumption is low, if but do not have suitable catalyzer, alkali lignin is degraded to single benzene ring type compounds in the water-based reaction system yield 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 single benzene ring type compounds yield greater than 10% method.
The present invention under the microwave cooperating effect, selects suitable CuO and Fe under the alkaline aqueous solution system
2(SO
4)
3Be catalyzer, with H
2O
2Or Na
2S
2O
8Be oxygenant, improved the degradation rate of xylogen and the yield of single benzene ring type compounds.
Purpose 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; May further comprise the steps:
1) water with 100 weight part alkali lignins and 660 weight parts joins in the microwave reaction tank, adds the NaOH of 26～130 weight parts, stirs, and adds the CuO of 3.3～33 weight parts, the Fe of 0.33～3.3 weight part again
2(SO
4)
3With the oxygenant of 27～1055 weight parts, the power that microwave reactor is set is 300～600W, and microwave frequency is 2450MHz ± 15Hz, carries out DeR 10～90min under 160～190 ℃; Described oxygenant is H
2O
2Or Na
2S
2O
8
2) cooling after reaction finishes is filtered, and adds H in the filtrate
2SO
4Solution is regulated pH value to 3～6, and the centrifugal insolubles of removing obtains containing the solution of single benzene ring type compounds.
Preferably, the alkali lignin step 1) is Wheat Straw Lignin from Alkali Pulping, bamboo alkali lignin, wood pulp alkali xylogen, bagasse alkali-lignin or the sahio base xylogen that the alkali paper-making pulping waste liquor reclaims.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 is to utilize microwave cooperating, has reduced temperature of reaction and reaction times, has solved lignin degradation and has prepared long reaction time in single phenyl ring class process, and temperature is high and produce easily the problem of biomass coking, under the microwave cooperating effect, with H
2O
2Or Na
2S
2O
8In water-based system, obtain the degradation rate of high alkali lignin and select suitable CuO and Fe as oxygenant
2(SO
4)
3Be catalyzer, improved 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 is introduced the degraded of microwave cooperating xylogen, and the reaction times is short, and efficient is high, compares with conventional high-temperature high pressure degradation technique, the advantage that need not to use high-tension apparatus, process to be easy to control, cost is low;
2, the present invention's reaction is with H in the water-based system
2O
2Or Na
2S
2O
8Be oxygenant, CuO and Fe
2(SO
4)
3Be catalyzer, need not with an organic solvent that catalyzer recycling capable of circulation has improved the degradation rate of alkali lignin and the yield of single benzene ring type compounds simultaneously greatly, has economy and environmental protection double effect.
Description of drawings
Fig. 1 is the liquid chromatogram that contains single benzene ring type compounds solution that obtains after the embodiment 1 described alkali lignin degraded.
Fig. 2 is the liquid chromatogram that contains the standard substance of single benzene ring compound in the degraded product.
Embodiment
Measure single benzene ring type compounds yield with efficient liquid phase chromatographic analysis among the present invention, analysis condition is as follows:
Adopt Prominence LC-20A type Shimadzu high performance liquid chromatograph, Agilent SB-C18 post, 40 ℃ of column temperatures, detector is UV-detector, detect wavelength 280nm, adopt ternary geopressure gradient elution process that product is carried out separation detection, mobile phase A is the phosphate aqueous solution of pH=2.0, B is methyl alcohol, and C is acetonitrile.The 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; Behind the 48min: V
A: V
B: V
C=100:0:0.
Degraded product is carried out liquid chromatography-mass spectrometry, determine respectively the molecular weight of recognizate, tentatively determine the title of single benzene ring substance in the degraded product according to molecular weight, then, choose the retention time that goes out the peak in the liquid chromatography of corresponding standard substance under same analysis condition, the concrete title of single benzene ring type compounds after the checking degraded.
The degradation rate of alkali lignin and the yield of single benzene ring type compounds calculate by following formula respectively:
Solid masses behind the add-on of the degradation rate %=(xylogen of alkali lignin-the reacted acid out)/add-on of alkali lignin * 100%
The add-on of the yield sum/alkali lignin of each single benzene ring type compounds of yield %=of single benzene ring type compounds * 100%.
Embodiment 1
The water of getting 100g sahio base xylogen and 660g joins in the microwave reaction tank, adds the NaOH of 26g, makes its dissolving, adds the CuO of 33g, the Fe of 3.3g again
2(SO
4)
3H with 1000g
2O
2, the power that microwave reactor is set is 300W, microwave frequency is 2450MHz; At 180 ℃ of lower degraded 60min; Cooling removed by filter catalyzer after reaction finished; The H that adds 1M
2SO
4, regulator solution pH value to 6, the centrifugal insolubles of removing obtains containing single benzene ring type compounds solution.
Fig. 1 is the liquid chromatogram that obtains product after embodiment 1 degraded, by with the contrast (Fig. 2) of the standard liquid chromatogram of single benzene ring type compounds, determine that single benzene ring type compounds is respectively in the degraded product of embodiment 1: 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 the reversed-phase liquid chromatography separation principle, the unknown peak that leading portion occurs in color atlas 1 should be the less polymerization degree that contains phenyl ring of polarity greater than 2 degraded product, and behind 42min, occur should be the stronger small molecules aliphatic chain organic acid substance of polarity.
Table 1 is the molecular weight of the material that detects according to degraded product liquid phase-mass spectrometry, the residence time and the concentration that the standard substance of definite related substances is determined through liquid chromatography and the typical curve equation that goes out peak area.
Table 1
Annotate: 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 according to the relation that goes out peak area and concentration (seeing Table 1) of liquid chromatography, calculates the yield of the various single benzene ring type compounds that obtain after being embodiment 1 degraded.
Obtain the yield of various single benzene ring type compounds after the degraded of table 2 alkali lignin
The yield of determining and obtaining various single benzene ring type compounds that following embodiment is relevant to contain single benzene ring type compounds determines that method with embodiment 1, does not provide one by one.
Embodiment 2
The water of getting 100g Wheat Straw Lignin from Alkali Pulping and 660g joins in the microwave reaction tank, adds the NaOH of 80g, makes its dissolving, adds the CuO of 3.3g, the Fe of 0.33g again
2(SO
4)
3With the mass concentration of 495g be 30% H
2O
2, the power that microwave reactor is set is 300W, microwave frequency is 2450MHz; At 180 ℃ of lower degraded 30min; Cooling removed by filter catalyzer after reaction finished; The H that adds 2M
2SO
4, regulator solution pH value to 3, the centrifugal insolubles of removing obtains containing single benzene ring type compounds solution.
Embodiment 3
The water of getting 100g wood pulp alkali xylogen and 660g joins in the microwave reaction tank, adds the NaOH of 106g, makes its dissolving, adds the CuO of 7g, the Fe of 0.7g again
2(SO
4)
3With the mass concentration of 600g be 30% H
2O
2, the power that microwave reactor is set is 300W, microwave frequency is 2450MHz; At 170 ℃ of lower degraded 20min; Cooling removed by filter catalyzer after reaction finished; The H that adds 2M
2SO
4, regulator solution pH value to 4, the centrifugal insolubles of removing obtains containing single benzene ring type compounds solution.
Embodiment 4
The water of getting 100g bagasse alkali-lignin and 660g joins in the microwave reaction tank, adds the NaOH of 130g, makes its dissolving, adds the CuO of 13g, the Fe of 1.3g again
2(SO
4)
3H with 850g
2O
2, the power that microwave reactor is set is 300W, microwave frequency is 2450MHz; At 160 ℃ of lower degraded 40min; Cooling removed by filter catalyzer after reaction finished; The H that adds 2M
2SO
4, regulator solution pH value to 6, the centrifugal insolubles of removing obtains containing single benzene ring type compounds solution.
Embodiment 5
The water of getting 100g bamboo alkali lignin and 660g joins in the microwave reaction tank, adds the NaOH of 50g, makes its dissolving, adds the CuO of 20g, the Fe of 2.0g again
2(SO
4)
3H with 1055g
2O
2, the power that microwave reactor is set is 300W, microwave frequency is 2450MHz; At 180 ℃ of lower degraded 40min; Cooling removed by filter catalyzer after reaction finished; The H that adds 2M
2SO
4, regulator solution pH value to 6, the centrifugal insolubles of removing obtains containing single benzene ring type compounds solution.
Embodiment 6
The water of getting 100g Wheat Straw Lignin from Alkali Pulping and 660g joins in the microwave reaction tank, adds the NaOH of 78g, makes its dissolving, adds the CuO of 3.3g, the Fe of 0.33g again
2(SO
4)
3H with 1055g
2O
2, the power that microwave reactor is set is 300W, microwave frequency is 2450MHz; At 190 ℃ of lower degraded 10min; Cooling removed by filter catalyzer after reaction finished; The H that adds 2M
2SO
4, regulator solution pH value to 6, the centrifugal insolubles of removing obtains containing single benzene ring type compounds solution.
Embodiment 7
The water of getting 100g Wheat Straw Lignin from Alkali Pulping and 660g joins in the microwave reaction tank, adds the NaOH of 78g, stirs, and makes its dissolving, adds the CuO of 13g, the Fe of 1.3g again
2(SO
4)
3Na with 27g
2S
2O
8, the power that microwave reactor is set is 300W, microwave frequency is 2450MHz; At 180 ℃ of lower degraded 90min; After reaction finished, cooling removed by filter catalyzer; The H that adds 2M
2SO
4, regulator solution pH value to 6, the centrifugal insolubles of removing obtains containing single benzene ring type compounds solution.
Comparative Examples 1
The water of getting 100g sahio base xylogen and 660g joins in the microwave reaction tank, adds the NaOH of 78g, stirs, and makes its dissolving, adds the H of 1000g again
2O
2, the power that microwave reactor is set is 300W, microwave frequency is 2450MHz; At 180 ℃ of lower degraded 60min; Cooling after reaction finishes, the H of adding 2M
2SO
4, regulator solution pH value to 6, the centrifugal insolubles of removing obtains containing single benzene ring type compounds solution.
Comparative Examples 2
The water of getting 100g sahio base xylogen and 660g joins in the microwave reaction tank, adds the NaOH of 78g, stirs, and makes its dissolving, adds the CuO of 13g again, and the power that microwave reactor is set is 300W, and microwave frequency is 2450MHz; At 180 ℃ of lower degraded 60min; Cooling after reaction finishes is filtered, and removes catalyzer; The H that adds 2M in the filtrate
2SO
4, regulator solution pH value to 6, the centrifugal insolubles of removing obtains containing single benzene ring type compounds solution.
Comparative Examples 3
The water of getting 100g sahio base xylogen and 660g joins in the microwave reaction tank, adds the NaOH of 78g, stirs, and makes its dissolving, adds the CuO of 13g, the Fe of 1.3g again
2(SO
4)
3, the power that microwave reactor is set is 300W, microwave frequency is 2450MHz; At 180 ℃ of lower degraded 60min; Cooling after reaction finishes is filtered, and removes catalyzer; The H that adds 2M in the filtrate
2SO
4, regulator solution pH value to 6, the centrifugal insolubles of removing obtains containing single benzene ring type compounds solution.
The implementation result explanation
Table 3 obtains the test data of yield and the alkali lignin degradation rate of single benzene ring type compounds for the embodiment of the invention.
The contrast of the data of table 3 alkali lignin degradation rate and single benzene ring compound yield
For implementation result of the present invention is described, with embodiment and under microwave cooperating separately oxidation or separately yield and the alkali lignin degradation rate of single benzene ring type compounds of obtaining of catalyzed degradation alkali lignin compare, contrast effect sees Table 3.
As can be seen from Table 3, under the 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 in the DeR system, do not use catalyzer of the present invention, independent hydrogen peroxide effect, although the degradation rate of alkali lignin can reach 85.57%, the yield of single benzene ring type compounds only is 2.52%(Comparative Examples 1); When reaction system is not used oxygenant, only add a kind of catalyzer or add two kinds of catalyzer, the degradation rate of alkali lignin all is lower than 50%, the yield of single benzene ring type compounds all is lower than 4%(Comparative Examples 2～3), all be far smaller than the resulting result of the inventive method, as seen the present invention prepares single benzene ring type compounds and has significant effect at the degraded alkali lignin, is that prior art is incomparable.
Claims (6)
1. microwave cooperating catalyzing oxidizing degrading alkali lignin prepares the method for single benzene ring type compounds; It is characterized in that may further comprise the steps:
1) water with 100 weight part alkali lignins and 660 weight parts joins in the microwave reaction tank, adds the NaOH of 26～130 weight parts, stirs, and adds the CuO of 3.3～33 weight parts, the Fe of 0.33～3.3 weight part again
2(SO
4)
3With the oxygenant of 27～1055 weight parts, the power that microwave reactor is set is 300～600W, and microwave frequency is 2450MHz ± 15Hz, carries out DeR 10～90min under 160～190 ℃; Described oxygenant is H
2O
2Or Na
2S
2O
8
2) cooling after reaction finishes is filtered, and adds H in the filtrate
2SO
4Solution is regulated pH value to 3～6, and the centrifugal insolubles of removing obtains containing the solution of single benzene ring type compounds.
2. preparation method according to claim 1 is characterized in that: step 1) in alkali lignin be Wheat Straw Lignin from Alkali Pulping, bamboo alkali lignin, wood pulp alkali xylogen, bagasse alkali-lignin or the sahio base xylogen that the alkali paper-making pulping waste liquor reclaims.
3. preparation method according to claim 1 is characterized in that: described H
2SO
4The concentration of solution is 1～2M.
4. oxygenant according to claim 1 is characterized in that: described H
2O
2Mass concentration be 30wt%.
5. preparation method according to claim 1 is characterized in that: described CuO and Fe
2(SO
4)
3Mass ratio be 10:1.
6. preparation method according to claim 1, it is characterized in that: the yield of described single benzene ring compound is greater than 10%, and the degradation rate of alkali lignin is greater than 90%.
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| CN103626642A (en) * | 2013-11-28 | 2014-03-12 | 上海应用技术学院 | Method for preparing vanillin |
| CN104910341A (en) * | 2015-06-24 | 2015-09-16 | 湖南师范大学 | Method for preparing lignin phenolic resin adhesive by treating papermaking waste liquid with microwave-CuO |
| CN106881113A (en) * | 2015-12-16 | 2017-06-23 | 中国石油化工股份有限公司 | A kind of biomass carbon sulfonic acid and preparation method thereof and the method with its catalytic esterification synthesizing adipic acid dibutyl ester |
| CN106946660A (en) * | 2017-02-07 | 2017-07-14 | 广西科学院 | A kind of method that utilization ammino-complex Catalytic lignin degraded prepares single phenolic compounds |
| CN106957211A (en) * | 2017-04-18 | 2017-07-18 | 中国科学技术大学 | A kind of method of catalytic degradation lignin |
| CN109824497A (en) * | 2019-03-06 | 2019-05-31 | 华南理工大学 | A kind of method that microwave cooperating catalysis of metalloporphyrin oxidative degradation alkali lignin prepares single benzene ring compound |
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| CN104910341A (en) * | 2015-06-24 | 2015-09-16 | 湖南师范大学 | Method for preparing lignin phenolic resin adhesive by treating papermaking waste liquid with microwave-CuO |
| CN106881113A (en) * | 2015-12-16 | 2017-06-23 | 中国石油化工股份有限公司 | A kind of biomass carbon sulfonic acid and preparation method thereof and the method with its catalytic esterification synthesizing adipic acid dibutyl ester |
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| CN110078877B (en) * | 2019-04-26 | 2021-07-27 | 福州大学 | Method for preparing dispersant by using lignin degradation product and application |
| 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 |
| CN110257097A (en) * | 2019-07-15 | 2019-09-20 | 中国林业科学研究院林产化学工业研究所 | A kind of method of microwave-assisted lignin hydrogenolysis preparation bio oil |
| 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 |
| CN111484405A (en) * | 2020-04-26 | 2020-08-04 | 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 |
| CN111495329A (en) * | 2020-04-26 | 2020-08-07 | 苏州纳创佳环保科技工程有限公司 | Method for synthesizing porous metal organic framework based on lignin degradation products |
| 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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