CN105085252A - Method for preparing phenolic acids by catalyzing and converting lignin through ionic liquid - Google Patents
Method for preparing phenolic acids by catalyzing and converting lignin through ionic liquid Download PDFInfo
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- CN105085252A CN105085252A CN201510498329.XA CN201510498329A CN105085252A CN 105085252 A CN105085252 A CN 105085252A CN 201510498329 A CN201510498329 A CN 201510498329A CN 105085252 A CN105085252 A CN 105085252A
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- C07—ORGANIC CHEMISTRY
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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Abstract
The invention discloses a method for preparing phenolic acids by catalyzing and converting lignin through ionic liquid. The method includes the following steps that (1) the lignin serves as a raw material, and lignin powder is obtained after the lignin is dried and smashed; (2) the ionic liquid is prepared, the lignin is processed and selectively catalyzed through the ionic liquid, and the phenolic acids are prepared; (3) a sample processed through the ionic liquid stands still and is adsorbed through macroporous resin, precipitate is washed through an ethanol solution, and the phenolic acids are obtained. The method builds a moderate system for processing the lignin in a solvent, microwaves, oil bath and other conditions are moderate in the processing process, the lignin can be converted into the phenolic acids in the system, large-scale application is facilitated, and the method is suitable for industrial production.
Description
Technical field
The present invention relates to and a kind ofly utilize ionic liquid-catalyzed conversion xylogen to prepare the method for phenolic acid, belong to biological chemical field.
Background technology
Society shortage of resources problem is day by day serious, and people start to develop new resources.Xylogen, mainly between cellulosic fibre, plays resistance to compression effect.In xylophyta, xylogen accounts for 25%, is the organism (Mierocrystalline cellulose is first) that second is the abundantest in the world.The waste of rich cellulose, the xylogen etc. such as stalk is renewable resources, can be used as bio-pharmaceutical, the raw material of the bio-based chemical productss such as bioenergy, is the effective way solving crisis of resource.Owing to there is aromatic base, phenolic hydroxyl group, alcoholic extract hydroxyl group, carbon back conjugated double bond isoreactivity group in the molecular structure of xylogen, therefore can carry out being oxidized, reduce, be hydrolyzed, alcoholysis, acidolysis methoxyl group, Suo Ji, photodissociation, phthalein, sulfonation, alkylation, halogenation, nitrated, many chemical reactions such as polycondensation or graft copolymerization.Its abundant carbon skeleton, on molecular structure, has and changes into various compound possibility.
Phenolic acid is the one of aldehydes matter, account for 1/3 of phenolic compound in plant derived foods, mostly be phenylformic acid and styracin through changing derivative, mainly exist with form that is free and constraint, the phenolic acid of constraint links together with vinegar key, ehter bond and chemical compound lot usually.The phenolic acid that lignin degradation produces is divided into 3 kinds of structure types: guaiacyl structure, Syringa oblata Lindl. based structures and to hydroxyphenyl structure.
Ionic liquid, as the salt of melting under a kind of room temperature or nearly room temperature condition, starts to be applied in the exploitation of cellulose materials in recent years, and achieve preliminary study progress, research in recent years shows that ionic liquid has good cellulose dissolution and processing power.They are different from typical organic solvent, electroneutral molecule is not had in ionic liquid, compared with traditional organic solvent, ionic liquid possesses non-volatile, low melting point, high stability, non-inflammability, the feature such as good conduction and thermal conductivity selective dissolution power, is called as " green solvent ".Ionic liquid replaces traditional organic solvent, has tempting prospect in environmental protect.In recent years, the ionic liquid research of new green environment protection more and more receives publicity.The complex construction that destruction Mierocrystalline cellulose and xylogen are combined closely, thus improve the degradation efficiency of complicated cellulose materials, be expected the production cost significantly reducing bioenergy, reach Efficient Conversion and utilize xylogen the like waste to prepare the object of bioenergy.Offset except environmental pollution and promotion biomass energy process of industrialization have important meaning.Because the research of many advantage ionic liquid process cellulose materialss becomes current study hotspot.
Summary of the invention
Goal of the invention: in order to overcome the deficiencies in the prior art, the invention provides and a kind ofly utilize ionic liquid-catalyzed conversion xylogen to prepare the method for phenolic acid, do not produce bazardous waste, process environmental protection in preparation process.
Technical scheme: for achieving the above object, of the present inventionly utilizes ionic liquid-catalyzed conversion xylogen to prepare the method for phenolic acid, comprises the following steps:
(1) take xylogen as raw material, under 50 ~ 100 DEG C of conditions, xylogen is dried and obtain xylogen powder;
(2) prepare ionic liquid, use ionic liquid to carry out Hybrid Heating stir process to the xylogen in xylogen powder, Catalytic lignin, the ratio of ionic liquid and xylogen is 10 ~ 50:1 by mass, obtained phenolic acid;
(3) use macroporous adsorbent resin to staticly settle phenolic acid, then adsorption precipitation, use volume percent to be that 30 ~ 60% ethanolic solns carry out wash-out separation to macroporous adsorbent resin, obtain phenolic acid further.
As preferably, in described step (1), xylogen is in grinding in ball grinder, crosses 200 mesh sieves and dry.
In described step (2), catalytic way is oil bath and microwave integrated process, first heating also magnetic agitation process in oil bath, and then microwave treatment.
Described oil bath Heating temperature is 130 ~ 160 DEG C, and the treatment time is 5 ~ 20min; Described microwave treatment Heating temperature is 160 ~ 210 DEG C, and the treatment time is 1 ~ 8min, and microwave power is 300-1000w.
Described step (2) intermediate ion liquid is 1-ethyl-3-methylimidazole diethyl phosphoric acid salt, 1-ethyl-3-methylimidazole acetate, 1-butyl-3-N-Methylimidazoleacetic salt, 1-amide group-3-N-Methylimidazoleacetic salt, 1-amide group-3-Methylimidazole villaumite, 1-methyl-3-Methylimidazole dimethyl phosphate salt, 1-methyl-3-Methylimidazole diethyl phosphoric acid salt, 1-ethyl-3-methylimidazole dimethyl phosphate salt, any one or a few combination of 1-butyl-3-Methylimidazole villaumite or 1-butyl-3-picoline villaumite.
In the present invention, macroporous adsorbent resin can be D101, AB-8, NKA-9, XAD4, XAD7HP and XAD1600 etc., all has good adsorption.Xylogen is carried out fragmentation by ionic liquid, impels the generation of phenolic acid functional group under certain oil bath, microwave condition.Ionic liquid provides the liquid environment of an environmental protection, macroporous resin then have cheap and easy to get and the feature such as can to reuse for reaction.
Beneficial effect: the present invention compared with prior art, has the following advantages:
(1) establish comparatively gentle xylogen system for handling in a solvent, the conditions such as the microwave in treating processes, oil bath are comparatively gentle, by lignin conversion phenolic acid, can be conducive to large-scale application, be suitable for suitability for industrialized production in this system;
(2) this system does not produce bazardous waste, process environmental protection;
(3) in reaction process use lignin dissolution functional ion liquid to act on xylogen, to be dissolved and fragmentation;
(4) macroporous adsorbent resin used in sepn process is cheap and easy to get and can reuse.
Accompanying drawing explanation
Fig. 1 is the MS figure of the vanillic acid that embodiment 4 obtains;
Fig. 2 is that the vanillic acid HPLC that embodiment 4 obtains schemes;
Fig. 3 is the vanillic acid structure elucidation figure that embodiment 4 obtains.
Embodiment
Below technical solution of the present invention is described in detail, but protection scope of the present invention is not limited to described embodiment.
Embodiment 1
(1) take xylogen as raw material, such as this lignin extraction is from maize straw, and by xylogen at ball mill grinding, cross 200 mesh sieves and drying, drying conditions is 50 ~ 100 DEG C, obtains xylogen powder;
(2) ionic liquid [EMIM] [DEP] is prepared, ionic liquid is used to carry out Hybrid Heating stir process to the xylogen in xylogen powder, Catalytic lignin composition, the ratio of ionic liquid and xylogen is 10:1 by mass, obtained phenolic acid sample;
(3) macroporous adsorbent resin D101 is used to staticly settle phenolic acid sample, then adsorption precipitation, use volume percent to be that 40% ethanolic soln carries out wash-out to macroporous adsorbent resin, elutriant, through rotary evaporation, obtains the solution of phenolic acid.
Embodiment 2
(1) with corn xylogen for raw material, by xylogen at ball mill grinding, cross 200 mesh sieves and dry, drying conditions is 80 DEG C, obtains xylogen powder;
(2) prepare ionic liquid [BMIM] [Ac], make this ionic liquid carry out Hybrid Heating stir process to the xylogen in xylogen powder, Catalytic lignin, ionic liquid mixes according to 30:1 ratio with corn xylogen powder by mass;
(3) ionic liquid process transforms xylogen: utilize ionic liquid that mixture is processed corn xylogen 20min under oil bath 150 DEG C of conditions, and magnetic agitation is even, then microwave treatment 2min under 640W, the condition of 180 DEG C, obtained phenolic acid sample;
(4) separation of phenolic acid: after ionic liquid process, macroporous adsorbent resin XAD7HP is used to staticly settle phenolic acid sample, then adsorption precipitation uses volume percent to be that 30% ethanolic soln carries out wash-out to macroporous adsorbent resin, elutriant, through 45 DEG C of underpressure distillation, obtains phenolic acid.
Embodiment 3
(1) with wheat xylogen for raw material, by xylogen at ball mill grinding, cross 200 mesh sieves and dry, drying conditions is 80 DEG C, obtains xylogen powder;
(2) prepare ionic liquid [BMIM] [Ac], make this ionic liquid carry out Hybrid Heating stir process to the xylogen in xylogen powder, Catalytic lignin, ionic liquid mixes according to 50:1 ratio with wheat xylogen powder by mass;
(3) ionic liquid process transforms xylogen: utilize ionic liquid that mixture is processed wheat xylogen 15min under oil bath 140 DEG C of conditions, and magnetic agitation is even, then microwave treatment 3min under 300W, the condition of 170 DEG C, obtained phenolic acid sample;
(4) separation of phenolic acid: after ionic liquid process, macroporous adsorbent resin NKA-9 is used to staticly settle phenolic acid sample, then adsorption precipitation uses volume percent to be that 50% ethanolic soln carries out wash-out to macroporous adsorbent resin, elutriant, through 45 DEG C of underpressure distillation, obtains phenolic acid.
Embodiment 4
(1) take xylogen as raw material, such as this lignin extraction is from maize straw, and by xylogen at ball mill grinding, cross 200 mesh sieves and drying, drying conditions is 100 DEG C, obtains xylogen powder;
(2) prepare ionic liquid 1-amide group-3-N-Methylimidazoleacetic salt, make this ionic liquid carry out Hybrid Heating stir process to the xylogen in xylogen powder, Catalytic lignin, mix according to 30:1 ratio with corn xylogen powder;
(3) sample obtained in step (2) is processed xylogen 5min under oil bath 160 DEG C of conditions, and magnetic agitation is even;
(4) microwave treatment: the sample above-mentioned oil bath handled well is microwave treatment 6min under 640W, the condition of 180 DEG C;
(5) separation of phenolic acid: after ionic liquid process, macroporous adsorbent resin is used to staticly settle phenolic acid, then adsorption precipitation, volume percent is used to be that 40% ethanolic soln carries out wash-out to macroporous adsorbent resin, elutriant, through rotary evaporation, obtains phenolic acid.
Carry out GC-MS and HPLC to obtained phenolic acid sample to detect, as depicted in figs. 1 and 2, the structure iron of sample is for shown in Fig. 3.Thus determine that this phenolic acid is vanillic acid.
Embodiment 5
When xylogen is 1g, when ionic liquid is ([EMIM] [Ac]) 30g and [MMIM] [DMP] 20g these two kinds mixing, oil bath temperature is 130 DEG C, time 10min, 210 DEG C of microwave treatment 2min, microwave power 1000w, other conditions are identical with embodiment 4, can obtain phenolic acid vanillic acid.
Embodiment 6
When xylogen is 1g, ionic liquid be [MMIM] [DMP] 10g, [BmpyM] [Cl] 10g and [BMIM] [Ac] 10g these three kinds mixing time, oil bath temperature is 160 DEG C, time 8min, 200 DEG C of microwave treatment time 1min, microwave power 800w, other conditions are identical with embodiment 4, can obtain acid vanillic acid.
Comparative example
Preparation ionic liquid [EMIM] DEP, this ionic liquid is made to carry out Hybrid Heating stir process Catalytic lignin to the xylogen in xylogen powder, 30g ionic liquid [EMIM] DEP and 0.15g xylogen mixes, be placed in microwave reactor, 100 DEG C are carried out microwave reaction 10min, and result can't detect phenolic acid.Without oil bath, directly carry out microwave catalysis, can not phenolic acid be obtained.
The above is only the preferred embodiment of the present invention; be noted that for those skilled in the art; under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (6)
1. utilize ionic liquid-catalyzed conversion xylogen to prepare a method for phenolic acid, its feature is being, comprises the following steps:
(1) take xylogen as raw material, under 50 ~ 100 DEG C of conditions, xylogen is dried and obtain xylogen powder;
(2) prepare ionic liquid, use ionic liquid to carry out Hybrid Heating stir process Catalytic lignin to the xylogen in xylogen powder, the ratio of ionic liquid and xylogen is 10 ~ 50:1 by mass, obtained phenolic acid sample;
(3) use macroporous adsorbent resin to staticly settle phenolic acid sample, then adsorption precipitation, use volume percent to be that 30 ~ 60% ethanolic solns carry out wash-out separation to macroporous adsorbent resin, obtain phenolic acid further.
2. according to claim 1ly utilize ionic liquid-catalyzed conversion xylogen to prepare the method for phenolic acid, it is characterized in that: in described step (1), xylogen is in grinding in ball grinder, cross 200 mesh sieves and dry.
3. according to claim 1ly utilize ionic liquid-catalyzed conversion xylogen to prepare the method for phenolic acid, it is characterized in that: in described step (2), catalytic way is oil bath and microwave integrated process, first heating also magnetic agitation process in oil bath, and then microwave treatment.
4. piece according to claim 3 utilize ionic liquid-catalyzed conversion xylogen to prepare the method for phenolic acid, it is characterized in that: described oil bath Heating temperature is 130 ~ 160 DEG C, the treatment time is 5 ~ 20min.
5. piece according to claim 3 utilize ionic liquid-catalyzed conversion xylogen to prepare the method for phenolic acid, it is characterized in that: described microwave treatment Heating temperature is 160 ~ 210 DEG C, the treatment time is 1 ~ 8min, and microwave power is 300-1000w.
6. the ionic liquid-catalyzed conversion xylogen that utilizes described in an any one of claim 1 to 5 prepares the method for phenolic acid, it is characterized in that: described step (2) intermediate ion liquid is 1-ethyl-3-methylimidazole diethyl phosphoric acid salt, 1-ethyl-3-methylimidazole acetate, 1-butyl-3-N-Methylimidazoleacetic salt, 1-amide group-3-N-Methylimidazoleacetic salt, 1-amide group-3-Methylimidazole villaumite, 1-methyl-3-Methylimidazole dimethyl phosphate salt, 1-methyl-3-Methylimidazole diethyl phosphoric acid salt, 1-ethyl-3-methylimidazole dimethyl phosphate salt, any one or a few combination of 1-butyl-3-Methylimidazole villaumite or 1-butyl-3-picoline villaumite.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108997151A (en) * | 2018-08-30 | 2018-12-14 | 济南大学 | The preparation method and products obtained therefrom of a kind of beta-unsaturated esters of alcohol-containing amine groups and application |
| CN109336774A (en) * | 2018-10-25 | 2019-02-15 | 华东师范大学 | The synthetic method and application of a kind of functionalization biology base ionic liquid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102924204A (en) * | 2012-11-06 | 2013-02-13 | 浙江大学 | Method for degrading and preparing micromolecule phenolic compound in ionic liquid by using microwave strengthened lignin |
| WO2014143657A1 (en) * | 2013-03-15 | 2014-09-18 | Suganit Systems, Inc. | Method of converting lignin and uses thereof |
| CN104387266A (en) * | 2014-12-10 | 2015-03-04 | 江苏科技大学 | Method for preparing straw active phenolic acid |
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- 2015-08-14 CN CN201510498329.XA patent/CN105085252A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924204A (en) * | 2012-11-06 | 2013-02-13 | 浙江大学 | Method for degrading and preparing micromolecule phenolic compound in ionic liquid by using microwave strengthened lignin |
| WO2014143657A1 (en) * | 2013-03-15 | 2014-09-18 | Suganit Systems, Inc. | Method of converting lignin and uses thereof |
| CN104387266A (en) * | 2014-12-10 | 2015-03-04 | 江苏科技大学 | Method for preparing straw active phenolic acid |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108997151A (en) * | 2018-08-30 | 2018-12-14 | 济南大学 | The preparation method and products obtained therefrom of a kind of beta-unsaturated esters of alcohol-containing amine groups and application |
| CN109336774A (en) * | 2018-10-25 | 2019-02-15 | 华东师范大学 | The synthetic method and application of a kind of functionalization biology base ionic liquid |
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Application publication date: 20151125 |