CN106883427B - Use CO2/H2The method of O system oxidation modification alkali lignin - Google Patents
Use CO2/H2The method of O system oxidation modification alkali lignin Download PDFInfo
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- CN106883427B CN106883427B CN201510930356.XA CN201510930356A CN106883427B CN 106883427 B CN106883427 B CN 106883427B CN 201510930356 A CN201510930356 A CN 201510930356A CN 106883427 B CN106883427 B CN 106883427B
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- alkali lignin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
Abstract
The present invention provides a kind of preparation methods of new type water-solubility lignin derivative.The present invention relates to CO2/H2The method of O system oxidation modification alkali lignin.With CO2/H2The acid system in situ that O is formed is as medium, under formates catalytic action, oxidative degradation alkali lignin.The present invention is cheap and easy to get, easy to operate with raw material, can be recycled, recycle the remarkable advantages such as simplicity.
Description
Technical field
The present invention relates to CO2/H2The acid system in situ that O is formed is as reaction medium, under formates catalytic action, oxygen
Change modified alkali lignin.
Background technique
Lignin is the biomass-based material that nature is only second to cellulose, and the whole world produces about 50,000,000,000 tons per year.Chinese conduct
Agricultural and forestry big country, up to 700,000,000 tons of annual agriculture and forestry organic waste material.One of main component therein is exactly lignin.People are daily
It also include lignin component in the industrial residue of waste and part that life generates.If therefore lignin cannot fill
Divide and utilize, one of primary pollution source will be will become, not only cause serious environmental pollution, and also result in the great wave of resource
Take.
Lignin molecule three-dimensional structure is complicated, included in organo-functional group be mostly polar group.It is especially more
Hydroxyl group form very strong intramolecular and intermolecular hydrogen bonding, cause lignin insoluble in any solvent.These properties make
The application of lignin in the industry is by very big restriction.In recent years, it is new to become lignin research and development for modified lignin resin
Hot spot direction.Such as lignosulfonates are exactly the more successful example of modified lignin resin, by means of its own stronger absorption
Property and interfacial activity, lignosulfonates are widely used in multiple fields such as printing and dyeing, rubber, water process.Therefore
A kind of environmentally friendly, safety easy to operate is developed, the high modified lignin resin method of Atom economy is particularly important.
The Chinese patent of Patent No. CN 102174202 disclose it is a kind of " a kind of water-soluble alkali lignin carboxylate and its
Preparation method ", this method prepare water-soluble alkali lignin in the presence of base catalyst, activator and Carboxylation reagent in water phase
Carboxylate.This method modified technique is complicated, and contains chlorine and bromide in Carboxylation reagent.
The Chinese patent of Patent No. CN 102250363 discloses " a kind of modification method of lignin ", and this method is that having
Demethylation reaction is carried out in solvent in the presence of mercaptan, basic catalyst, and then achievees the purpose that modified lignin resin.Many institutes
Known, mercaptan has strong corrosiveness to equipment, brings security risk to production.
Summary of the invention
It is an object of the invention to utilize CO2/H2O system catalysis oxidation prepares a kind of novel water-soluble alkali lignin.Change
Property after alkali lignin have high level carbonyl, therefore have good water solubility.
To achieve the above object, the invention adopts the following technical scheme:
From the preparation method of modified alkali lignin: in CO2/H2In O system, temperature, pressure and formates catalysis appropriate
Under effect, oxidative degradation alkali lignin；
The catalyst can appoint for sodium formate, potassium formate, calcium formate, copper formate, the one or more of magnesium formate
Meaning ratio；In use, the mass concentration range of catalyst is between 0.001-5% in system, preferred mass concentration range
Between 0.1-1%；
Reaction temperature >=100 DEG C, preferably 125-180 DEG C；Reaction time is no less than 0.5h, preferably 3-12h；Carbon dioxide
With oxygen gross pressure 0.1-13MPa；It is preferred that pressure is 2-6MPa；The mass concentration range of lignin additional amount exists in system
Between 0.1-100%, preferably the mass concentration range of lignin additional amount is between 1-5%；
The present invention has the advantage that: 1) in water phase, directly that living resources (instead of fossil resource) is modified, raw material can
Regeneration, it is at low cost, and sustainable development.2) it is introduced without element sulphur, the alkali lignin modified water for hydrophilic carbonyldioxy composition
Dissolubility lignin derivative.3) subsequent processes and waste is avoided to generate.
Detailed description of the invention
Fig. 1 is infrared spectrogram.
Specific embodiment
Following implementation will be helpful to understand the present invention, but protection scope of the present invention is not limited to these examples:
Agents useful for same is as follows in embodiment:
Alkali lignin: Shandong Longli Biology Science and Technology Co., Ltd
Formates: Tianjin Ke Miou chemical reagent Co., Ltd
Embodiment 1
300ml pressure reaction still is added in 2 grams of alkali lignins, while 0.3 gram of sodium formate and 100ml being added into reaction kettle
Water, enclosed high pressure kettle are then passed to carbon dioxide and oxygen (pressure ratio 1.5:1) by replacement of oxygen 3 times, maintain reaction
Gross pressure is 5.0MPa, after autoclave is heated to 150 DEG C, reaction 8 hours through 45 minutes, stops reaction, is down to room temperature, beats
Opening blow valve makes pressure in kettle be down to normal pressure.Deposit-free occurs after reaction.
Embodiment 2
50ml pressure reaction still is added in 0.2 gram of alkali lignin, while 0.03 gram of potassium formate and 10ml being added into reaction kettle
Water, enclosed high pressure kettle lead to replacement of oxygen 3 times, then pass to carbon dioxide and oxygen (pressure ratio 1.5:1), maintain reaction total
Pressure is 5.0MPa, after autoclave is heated to 150 DEG C, reaction 8 hours through 25 minutes, stops reaction, is down to room temperature, opening is put
Empty valve makes pressure in kettle be down to normal pressure.Deposit-free occurs after reaction.
Embodiment 3-10
50ml pressure reaction still is added in a certain amount of alkali lignin, while a certain amount of sodium formate and 10ml being added into reaction kettle
Water, enclosed high pressure kettle lead to replacement of oxygen 3 times, then pass to carbon dioxide and oxygen (pressure ratio 1:1), maintain reaction stagnation pressure
Power is 5.0MPa, and autoclave is heated to certain temperature after reaction 8 hours and stops reaction, is down to room temperature, opening blow valve makes
Pressure is down to normal pressure in kettle.The lignin filtering not converted completely, weighs after dry.Reaction result is detailed in following table.
Embodiment 11
Modified lignin resin and unmodified lignin elemental analysis Comparative result see the table below:
| C% | H% | O% | S% | N% | |
| Alkali lignin | 61.8 | 6.178 | 29.072 | 0.6 | 2.35 |
| Modified alkali lignin | 29.77 | 3.187 | 64.258 | 0.675 | 2.11 |
In infrared spectrogram, the infrared signature diffraction maximum position of modified alkali lignin is similar with former alkali lignin, not compared with
Big difference, illustrates that modified-reaction does not destroy the basic structure of alkali lignin.But in conjugation carbonyl diffraction maximum position 1662cm-1, the absorption intensity of modified alkali lignin has significant raising compared with former alkali lignin, illustrates to be carbonylated modified-reaction in alkali
More conjugation carbonyls are introduced in lignin molecule.In addition, passing through the elemental analysis ratio to alkali lignin and modified alkali lignin
Compared with as can be seen, the average oxygen content of modified alkali lignin is significantly improved.
Claims (8)
1. using CO2/H2The method of O system oxidation modification alkali lignin, it is characterised in that:
Using alkali lignin as reaction raw materials, with CO2/H2The acid system in situ that O is formed is catalyzed in formates and makees as reaction medium
Oxidation reaction is carried out under；Reaction temperature >=100 DEG C, reaction time are no less than 0.5h, and carbon dioxide and oxygen gross pressure is
0.1-13MPa；
Catalyst and alkali lignin mass concentration ratio are between 0.1-100% range.
2. according to the method for claim 1, it is characterised in that:
The catalyst: one of sodium formate, potassium formate, calcium formate, copper formate, magnesium formate or two kinds or more.
3. according to the method for claim 2, it is characterised in that:
The catalyst: sodium formate.
4. according to the method for claim 1, it is characterised in that:
The mass concentration of catalyst is between 0.1-1% range in catalystic converter system.
5. according to the method for claim 1, it is characterised in that:
100-250 DEG C of reaction temperature；Reaction time 0.5-24h；CO2Pressure is 0.1-5MPa；Oxygen pressure is 0.1-5MPa；Two
Carbonoxide and oxygen pressure ratio are 1:1-4:1；Carbon dioxide and oxygen gross pressure 1-10MPa.
6. according to the method for claim 5, it is characterised in that:
Reaction temperature is 125-180 DEG C；Reaction time is 4-12h；Carbon dioxide and oxygen gross pressure 2-6MPa.
7. according to the method for claim 1, it is characterised in that:
The mass concentration of alkali lignin is between 0.1-100% in system.
8. according to the method for claim 7, it is characterised in that:
The mass concentration of alkali lignin is between 1-5% in system.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0649223A (en) * | 1992-08-03 | 1994-02-22 | Mokushitsu Shinsozai Gijutsu Kenkyu Kumiai | Carboxyalkylated lignin derivative |
| CN101824154A (en) * | 2010-04-23 | 2010-09-08 | 北京嘉禾木科技有限公司 | Preparation method of carboxylated lignin |
| CN102174202A (en) * | 2011-03-18 | 2011-09-07 | 华南理工大学 | Water-soluble alkali lignin carboxylate and preparation method thereof |
| CN102660035A (en) * | 2012-05-22 | 2012-09-12 | 东北林业大学 | Method for catalyzing, degrading and also activating alkali lignin by utilizing mixed system of phosphotungstic acid and H2O2 |
| CN103709772A (en) * | 2013-12-16 | 2014-04-09 | 华南理工大学 | Inorganic/lignin-series polymer composite nano-particles as well as preparation method and application thereof |
| JP2014208333A (en) * | 2013-03-26 | 2014-11-06 | 独立行政法人産業技術総合研究所 | Method of producing metal scavenger including oxidized lignin, metal scavenger including oxidized lignin, method of removing metal in aqueous solution, and method of enhancing metal-scavenging performance of lignin |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013036911A1 (en) * | 2011-09-09 | 2013-03-14 | University Of Tennessee Research Foundation | Metal catalyzed oxidation of lignin and related compounds |
| US9359391B2 (en) * | 2014-03-14 | 2016-06-07 | Wisconsin Alumni Research Foundation | Selective C—O bond cleavage of oxidized lignin and lignin-type materials into simple aromatic compounds |
-
2015
- 2015-12-15 CN CN201510930356.XA patent/CN106883427B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0649223A (en) * | 1992-08-03 | 1994-02-22 | Mokushitsu Shinsozai Gijutsu Kenkyu Kumiai | Carboxyalkylated lignin derivative |
| CN101824154A (en) * | 2010-04-23 | 2010-09-08 | 北京嘉禾木科技有限公司 | Preparation method of carboxylated lignin |
| CN102174202A (en) * | 2011-03-18 | 2011-09-07 | 华南理工大学 | Water-soluble alkali lignin carboxylate and preparation method thereof |
| CN102660035A (en) * | 2012-05-22 | 2012-09-12 | 东北林业大学 | Method for catalyzing, degrading and also activating alkali lignin by utilizing mixed system of phosphotungstic acid and H2O2 |
| JP2014208333A (en) * | 2013-03-26 | 2014-11-06 | 独立行政法人産業技術総合研究所 | Method of producing metal scavenger including oxidized lignin, metal scavenger including oxidized lignin, method of removing metal in aqueous solution, and method of enhancing metal-scavenging performance of lignin |
| CN103709772A (en) * | 2013-12-16 | 2014-04-09 | 华南理工大学 | Inorganic/lignin-series polymer composite nano-particles as well as preparation method and application thereof |
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