CN103819310B - Method for degrading lignin in seawater - Google Patents
Method for degrading lignin in seawater Download PDFInfo
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- CN103819310B CN103819310B CN201210462422.1A CN201210462422A CN103819310B CN 103819310 B CN103819310 B CN 103819310B CN 201210462422 A CN201210462422 A CN 201210462422A CN 103819310 B CN103819310 B CN 103819310B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
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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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/42—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms in positions 2 and 4
- C07D311/44—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms in positions 2 and 4 with one hydrogen atom in position 3
- C07D311/46—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms in positions 2 and 4 with one hydrogen atom in position 3 unsubstituted in the carbocyclic ring
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Abstract
The invention discloses a method for degrading lignin in seawater. The method comprises the following steps: at the temperature of 150-500 DEG C, after the lignin is mixed with the seawater for reaction for no less than 0.5 h, separating to obtain the mixed product of phenolic compounds, wherein the total weight of the mixed product of the phenolic compounds accounts for more than 20% of the weight of the lignin in feeding materials. The method has the advantages of wide source of raw materials, simplicity in separation, high product yield and the like, and is suitable for preparing the phenolic compounds such as coniferyl alcohol, tonquinol, vanillic aldehyde, syringyl derivatives and the like by using biomass resources as raw materials.
Description
Technical field
The invention belongs to energy field, be specifically related to the method for lignin degrading in a kind of seawater
Background technology
Reduce along with carbonaceous subterranean resource and utilize difficulty to increase, human needs seeks continuable ground carbon resource, to realize the Sustainable development of zero carbon emission of ground off-balancesheet.Xylogen be the earth comes Mierocrystalline cellulose, chitin after amount be the 3rd organic carbon resource, estimate that the annual whole world can produce 1,500 hundred million tons of xylogen by plant-growth, Utilization prospects is wide.The basic structural unit of xylogen contains aromatic ring structure, is the material uniquely in sustainable carbon resource with aromatic ring structure, be substitute and supplement existing take fossil resource as one of raw material important channel of preparing aromatic compound.
The current Application way of xylogen make use of the character such as high-energy (boiler combustion), polarity polyfunctional group (building materials, oil field), carbon containing (thermo-cracking, hydrogenation deoxidation) of xylogen, destroys the aromatic ring structure of its uniqueness.Xylogen is the three-dimensional macromolecular compound be formed by connecting by C-C key and ehter bond by phenyl-propane class formation unit, and ether-oxygen bond of selecting to dissociate obtains to have the key of aromatic ring monomer compound.The method of document and patent report, in strong acid, highly basic, particle liquid, supercritical solvent or organic solvent, realizes the fracture of ether-oxygen bond.Patent CN101680167A discloses a kind of degradation method of xylogen, under heteropoly acid catalysis, is with an organic solvent the compound of 1-3 benzene ring structure by lignin conversion, comprises Vanillin and derivative etc. thereof.It is the method for liquid fuel by lignin conversion that patent CN102548935A discloses a kind of, under load type metal catalyst, generates saturated and/or fractional saturation hydrocarbon as the mix products of naphthalene, paraffinic hydrocarbons, alkene, diolefine etc.Article (J.Am.Chem.Soc., 2011,133, pp 14090-14097) reports employing supercritical CO
2reaction system and C20 PMO catalyzer, transform xylogen to naphthenic hydrocarbon.But these method raw materials cost and separation costs higher, especially thermo-cracking and hydrocracking route, destroy benzene ring structure, reduce its utility value.
Wood Adhesives from Biomass utilizes should not strive tap water with the mankind.Seawater takes up an area 97.4% of ball water resources, contains the materials such as abundant inorganic salt, amino acid, drink and utilize cost high, but it is as industrial process waters because of it, and it is low to take cost.Salinity in seawater can be used as the catalyzer of lignin degrading, and low cost prepares high added value phenolic compound.
Summary of the invention
The object of this invention is to provide a kind of low cost prepares high added value phenolic compound method from xylogen.This method is significantly different with the method reported up to now.This process does not need additionally to add catalyzer, and only need seawater and xylogen hybrid reaction, can obtain organic liquid product after separation, yield is greater than 20%.Salinity in seawater plays katalysis.Xylogen ether-oxygen bond and carbon-carbon bond fracture can be undertaken by following path.At a certain temperature, salinity plays the effect of polarized water molecule, for ether-oxygen bond fracture provides ripple hydrogen alive or ripple hydroxyl of living.These active species attack ether-oxygen bond and carbon-carbon bond, make it fracture, but due to its limited activity, the C (sp of phenyl ring
2)-H key and aromaticity structure remain, generation phenolic compound is primary product.
Xylogen is wide in occurring in nature source, although existence form is diversified, basic structural unit is similar.Xylogen etc. after xylogen after sodium lignosulfonate in xylogen, the paper mill waste material such as root, stem, leaf, skin, fruit shell of natural phant and alkali lignin, employing solvent extraction, biological treatment all can be used as raw material sources.The relative molecular weight of log quality reaches hundreds of thousands of to millions of, and the distribution of relative molecular weight is very wide, but the relative molecular weight of separating lignin is much lower, is generally several thousand to several ten thousand, and this is mainly relevant with the selectivity scission of link being separated solvent molecule.As adopted unsegregated log quality, needing active higher reaction species to penetrate in the structure of xylogen densification, react with oxy radical, realize scission of link, and this permeable reactive process not only depending on the source of log xylogen, more relevant to the activity of species.The content of xylogen adopts Klason method to measure.
The present invention adopts natural sea-water or artificial seawater as reaction system, although the concrete chemical process related to is not yet clear, the salinity in seawater has material impact to this process.Natural sea-water source is wide, and the concentration of the salt dissolved regardless of seawater, the ratio wherein between Ordinary ion is always constant.In its composition, main component is greater than 1 × 10
6mg/(kilogram of seawater) positively charged ion have Na
+, K
+, Ca
2+, Mg
2+and Sr
2+, negatively charged ion has Cl
-, SO
4 2-, Br
-, HCO
3 -(CO
3 2-) and F
-, and H
3bO
3.At reaction conditions, there is noticeable change, as polarizability etc., xylogen can well be dissolved and transform in these ions.And engulf free radical due to these ions, product is difficult to Raolical polymerizable occurs, and selectivity of product is improved.
Lignin conversion needs just can carry out at high temperature.At critical with close under critical condition, the series of properties sudden change of water, as solubility property increases, soda acid performance change etc., contribute to dissolving and the conversion of xylogen.But too high temperature of reaction can cause product to be polymerized and coking.The temperature of reaction that suggestion adopts is 150-500 ° of C, and preferred temperature is 200-350 ° of C, and optimum temps is 250-300 ° of C.At this temperature, reaction vessel is needed to have certain withstand voltage properties, as autoclave, reaction under high pressure pipe etc. can be adopted.But the security of high temperature seawater is higher than the organic solvent (as alcohol, alkane etc.) in existing method, and running cost is lower.
Xylogen can mix with seawater in principle in any proportion.High lignin charging capacity, increases production efficiency, but simultaneously due to the relative minimizing of seawater consumption, mass transfer and the heat transfer of reaction system weaken, and the occurrence probability of coking polyreaction increases.But content of lignin is too low, production efficiency reduces.The suggestion weight percent that middle xylogen accounts for seawater that feeds intake is 0.01 ~ 70%, and be preferably 5 ~ 50%, the best is 15 ~ 30%.
The reaction of xylogen and seawater is a recombination process dissolving and transform.Wherein xylogen effectively dissolves is the basic of reaction generation.Lignin dissolution is the process of a kinetic control, the generation of active specy and the infiltration in xylogen dense structure thereof and reaction, closely related with the reaction times.The best reaction times should be the maximum value that xylogen is converted into phenolic compound productive rate completely, and the continuation prolongation reaction times increases side reaction on the contrary.The proposal reactions time is not less than 0.5 hour, and the better time is 1 ~ 20 hour, and Best Times is 2-8 hour.
Reaction after product and seawater form the two-phase of layering, and after adding organic solvent, by product extraction in solvent, after a small amount of repeatedly extraction, in seawater, the content of product is very low.Primary product is present in organic solvent.Conventional extraction agent can be in chloroform, methylene dichloride, hexanaphthene, ether, sherwood oil, toluene, benzene, dioxane, ethyl acetate etc. one or more.Through distillation except after desolventizing, extraction agent can be recycled.Primary product is phenolic compound.In view of the difference of content of lignin in raw material and the complicacy of product, transformation efficiency and optionally accurate calculating are more difficult.Under study for action, adopt and be separated the percentages that the gross weight obtaining organic liquid product accounts for xylogen weight in input material, to quantize reaction efficiency.Product, primarily of phenolic compound compositions such as lubanol, tonquinol, Vanillin, Syringa oblata Lindl. radical derivatives, accounts for and drops into more than 20% of xylogen weight in material.
Compared with method in the past, the present invention has following advantage:
(1) raw material sources are wide, and cost is low
(2) product separation is simple, and resource can reuse
(3) simple to operate
Instant invention overcomes the feature adopting the organic solvent of high cost and non-common solvents in invention in the past, when additionally not adding catalyzer, realizing xylogen conversion in the seawater, operational safety, is the method for a promising conversion xylogen of tool.
Embodiment
Embodiment 1
By 10g Alcell xylogen and 100 milliliters of natural sea-water mixing, transfer to (Parr4740) in autoclave.After nitrogen replacement air 3-5 time, be heated to 260 ° of C.React after 8 hours, stop stirring, drop to room temperature, divide after adding 40mL chloroform extraction reaction soln for 3 times respectively and merge, it is 9.0 grams that distillation obtains liquid organic mixture, accounts for 90% of charging capacity.Product is through chromatograph-mass spectrometer coupling analysis, and primary product is lubanol (40%), tonquinol (35%), Vanillin (12%), Syringa oblata Lindl. radical derivative (8%), and other products 5%(comprises dipolymer and trimer).
Embodiment 2
By 3g Alcell xylogen and 10 milliliters of sea water mixing, transfer to (Swagelokminitube) in pressure-tight container.After nitrogen replacement air 3-5 time, be heated to 350 ° of C.React after 20 hours, stop stirring, drop to room temperature, divide after adding 40mL petroleum ether extraction reaction soln for 3 times respectively and merge, it is 2.5 grams that distillation obtains liquid organic mixture, accounts for 83% of charging capacity.Product is through chromatograph-mass spectrometer coupling analysis, and primary product is lubanol (38%), tonquinol (36%), Vanillin (15%), Syringa oblata Lindl. radical derivative (6%), and other products 5%(comprises dipolymer and trimer).From the experimental results, use same raw material, change the impact of reaction conditions on products distribution less, the ratio of product unit is determined by the character of xylogen itself.
Embodiment 3
By 6g Alcell xylogen and 10 milliliters of sea water mixing, transfer to (Swagelokminitube) in pressure-tight container.After nitrogen replacement air 3-5 time, be heated to 350 ° of C.React after 20 hours, stop stirring, drop to room temperature, divide after adding 40mL petroleum ether extraction reaction soln for 3 times respectively and merge, it is 3.2 grams that distillation obtains liquid organic mixture, accounts for 53% of charging capacity.Product is through chromatograph-mass spectrometer coupling analysis, and primary product is lubanol (34%), tonquinol (35%), Vanillin (17%), Syringa oblata Lindl. radical derivative (5%), other products 9%(comprise dipolymer and trimer).From the experimental results, improve the consumption of xylogen, the yield of organic liquid product obviously reduces, and the amount of polymer also has increase.
Embodiment 4
By 3g Aldrich xylogen and 10 milliliters of sea water mixing, transfer to (Swagelokminitube) in pressure-tight container.After nitrogen replacement air 3-5 time, be heated to 300 ° of C.React after 10 hours, stop stirring, drop to room temperature, divide after adding 40mL xylene extraction reaction soln for 3 times respectively and merge, it is 2.2 grams that distillation obtains liquid organic mixture, accounts for 71% of charging capacity.Primary product is lubanol (28%), tonquinol (15%), Vanillin (33%), Syringa oblata Lindl. radical derivative (19%), other products 5%(comprise dipolymer and trimer).
Embodiment 5
By 2g Aldrich xylogen and 10 milliliters of sea water mixing, transfer to (Swagelokminitube) in pressure-tight container.After nitrogen replacement air 3-5 time, be heated to 300 ° of C.React after 10 hours, stop stirring, drop to room temperature, divide after adding 40mL xylene extraction reaction soln for 3 times respectively and merge, it is 2.2 grams that distillation obtains liquid organic mixture, accounts for 71% of charging capacity.Product is through chromatograph-mass spectrometer coupling analysis, and primary product is lubanol (28%), tonquinol (15%), Vanillin (33%), Syringa oblata Lindl. radical derivative (19%), other products 5%(comprise dipolymer and trimer).
Embodiment 6
By 2g aspen quality (scientific research KTH) and 50 milliliters of sea water mixing, transfer to (Parr 4740) in autoclave.After nitrogen replacement air 3-5 time, be heated to 150 ° of C.React after 15 hours, stop stirring, drop to room temperature, divide after adding 40mL chloroform extraction reaction soln for 3 times respectively and merge, it is 0.9 gram that distillation obtains liquid organic mixture, accounts for 45% of charging capacity.Product is through chromatograph-mass spectrometer coupling analysis, and primary product is lubanol (34%), tonquinol (30%), Vanillin (10%), Syringa oblata Lindl. radical derivative (21%), other products 5%(comprise dipolymer and trimer).
Embodiment 7
By 5g sodium lignosulfonate (Clariant SAS60) and 30 milliliters of sea water mixing, transfer to (Parr 4740) in autoclave.After nitrogen replacement air 3-5 time, be heated to 250 ° of C.React after 8 hours, stop stirring, drop to room temperature, divide after adding 40mL chloroform extraction reaction soln for 3 times respectively and merge, it is 2.1 grams that distillation obtains liquid organic mixture, accounts for 42% of charging capacity.Product is through chromatograph-mass spectrometer coupling analysis, and primary product is lubanol (28%), tonquinol (25%), Vanillin (17%), Syringa oblata Lindl. radical derivative (19%), other products 11%(comprise dipolymer and trimer).
Embodiment 8
By 2g Kraft xylogen (Aldrich) and 10 milliliters of sea water mixing, transfer to (Swagelok minitube) in autoclave.After nitrogen replacement air 3-5 time, be heated to 250 DEG C.React after 8 hours, stop stirring, drop to room temperature, divide after adding 40mL chloroform extraction reaction soln for 3 times respectively and merge, it is 2.1 grams that distillation obtains liquid organic mixture, accounts for 42% of charging capacity.Product is through chromatograph-mass spectrometer coupling analysis, and primary product is lubanol (24%), tonquinol (31%), Vanillin (15%), Syringa oblata Lindl. radical derivative (16%), other products 14%(comprise dipolymer and trimer).
Embodiment 9
By seawater used in embodiment 1 after extracting and separating, directly add the Alcell xylogen with embodiment 1 same amount, carry out reaction according to the method for embodiment 1.The reacted liquid organic mixture that obtains is 8.8 grams, accounts for 88% of charging capacity.Close with the result of embodiment 90%, illustrate that reacted seawater can be reused.Primary product is lubanol (41%), tonquinol (34%), Vanillin (12%), Syringa oblata Lindl. radical derivative (7%), other products 6%(comprise dipolymer and trimer).
Embodiment 10
Prepare the composed as follows of artificial seawater.Chlorine ion concentration 22g/L, calcium ion concn 1.3g/L, magnesium ion concentration 1.9g/L, boric acid 1.0g/L.Medicine adopts analytically pure sodium-chlor, sodium carbonate (with sodium-chlor molar ratio 1:2), magnesium sulfate, nitrocalcite and boric acid.Carry out reaction according to embodiment 1, the reacted liquid organic mixture that obtains is 7.5 grams, accounts for 75% of charging capacity.Product is through chromatograph-mass spectrometer coupling analysis, and primary product is lubanol (34%), tonquinol (35%), Vanillin (18%), Syringa oblata Lindl. radical derivative (7%), other products 6%(comprise dipolymer and trimer).
Claims (9)
1. the method for lignin degrading in seawater, at 150-500 DEG C of temperature, reacts after being not less than 0.5 hour by xylogen and sea water mixing, is separated the mix products obtaining phenolic compound; The weight percent that the middle xylogen that feeds intake accounts for seawater is 0.01 ~ 70%.
2. in accordance with the method for claim 1, described phenolic compound is one or two or more kinds in lubanol, tonquinol, Vanillin, Syringa oblata Lindl. radical derivative.
3. in accordance with the method for claim 1, described seawater refers to natural sea-water or artificial seawater.
4. in accordance with the method for claim 1, temperature of reaction is 200-350 DEG C, and the reaction times is 1 ~ 20 hour;
5., according to the method described in claim 1 or 4, temperature of reaction is 250 DEG C ~ 300 DEG C, and the reaction times is 2-8 hour.
6. in accordance with the method for claim 1, the weight percent that the middle xylogen that feeds intake accounts for seawater is 5 ~ 50%,
7., according to the method described in claim 1 or 6, the weight percent that the middle xylogen that feeds intake accounts for seawater is 15 ~ 30%.
8. xylogen raw material in accordance with the method for claim 1, used is: one or two or more kinds in the xylogen after the xylogen in the root of natural phant, stem, leaf, skin, fruit shell, the sodium lignosulfonate in the waste material of paper mill and alkali lignin, employing solvent extraction, the xylogen after biological treatment; In xylogen raw material, the weight content of xylogen is 1-100%.
9. in accordance with the method for claim 1, product separation method is: reacted liquid is added extraction agent extraction product, extraction agent is one or two or more kinds in chloroform, methylene dichloride, ether, sherwood oil, toluene, benzene, dioxane, after extraction agent is separated, after distillation removing extraction agent, obtain mix products; Primary product is phenolic compound; The gross weight that separation obtains organic product accounts for more than 20% of xylogen weight in input material.
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| CN201210462422.1A CN103819310B (en) | 2012-11-16 | 2012-11-16 | Method for degrading lignin in seawater |
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| CN201210462422.1A CN103819310B (en) | 2012-11-16 | 2012-11-16 | Method for degrading lignin in seawater |
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| CN103819310B true CN103819310B (en) | 2015-07-15 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105969822A (en) * | 2016-06-08 | 2016-09-28 | 华南理工大学 | Lignocellulose pretreatment method based on ionic liquid |
| CN111348988B (en) * | 2018-12-21 | 2022-12-02 | 北京林业大学 | Method for preparing coniferyl alcohol, sinapyl alcohol and derivatives thereof from lignocellulose |
| CN111689932A (en) * | 2020-07-17 | 2020-09-22 | 中国林业科学研究院林产化学工业研究所 | Method for preparing furan derivative by seawater catalysis and oriented liquefaction of wood fiber biomass |
Citations (3)
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|---|---|---|---|---|
| CN102173980A (en) * | 2011-03-18 | 2011-09-07 | 华南理工大学 | Method for preparing phenolic chemicals through thermo-chemical conversion of industrial lignin |
| CN102199086A (en) * | 2010-03-24 | 2011-09-28 | 淮北中润生物能源技术开发有限公司 | Method for synchronously hydrolyzing cellulosic biomass |
| CN102476980A (en) * | 2010-11-30 | 2012-05-30 | 中国科学院大连化学物理研究所 | Application of tungsten-based catalyst in lignin catalytic hydrogenation for producing aromatic compound |
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Patent Citations (3)
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| CN102199086A (en) * | 2010-03-24 | 2011-09-28 | 淮北中润生物能源技术开发有限公司 | Method for synchronously hydrolyzing cellulosic biomass |
| CN102476980A (en) * | 2010-11-30 | 2012-05-30 | 中国科学院大连化学物理研究所 | Application of tungsten-based catalyst in lignin catalytic hydrogenation for producing aromatic compound |
| CN102173980A (en) * | 2011-03-18 | 2011-09-07 | 华南理工大学 | Method for preparing phenolic chemicals through thermo-chemical conversion of industrial lignin |
Non-Patent Citations (2)
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| 木质素磺酸盐在UV/H2O2下的降解;王雪莲等;《林产化学与工业》;20070630;第27卷(第3期);98-102 * |
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