CN103554400A - Liquefaction method of lignin for preparing thermoplastic phenolic resin - Google Patents
Liquefaction method of lignin for preparing thermoplastic phenolic resin Download PDFInfo
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- CN103554400A CN103554400A CN201310476940.3A CN201310476940A CN103554400A CN 103554400 A CN103554400 A CN 103554400A CN 201310476940 A CN201310476940 A CN 201310476940A CN 103554400 A CN103554400 A CN 103554400A
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Abstract
The invention discloses a liquefaction method of lignin for preparing a thermoplastic phenolic resin. The liquefaction method is as follows: mixing phenol, a heteropoly acid catalyst and enzymatic hydrolysis lignin, heating to 90-160 DEG C, and liquefying for 1-3 h to obtain a liquefied product. The invention provides an efficient method for preparing a phenolic compound used for substituting phenol by using enzymolysis lignin in abundant resource, and the method uses the a green heteropoly acid catalyst, which has no pollution to the environment. The enzymolysis lignin liquefaction product obtained by the invention can be used in the preparation of a lignin base thermoplastic phenolic resin.
Description
Technical field
The present invention relates to a kind of liquifying method of the xylogen for the preparation of novolac resin, relate in particular to a kind of novel acid catalyst for the method for liquefying lignin modification.
Background technology
Xylogen (lignin) is in the unique non-oil resource ，Shi vegitabilia that renewable aryl compound can be provided of nature, to be only second to cellulosic the second abundant natural polymer.Lignin molecule has numerous different types of active groups, has renewable, degradable, the advantage such as nontoxic concurrently.Enzymolysis xylogen (Enzymatic Hydrolysis Lignin is called for short EHL) is the Novel wooden quality of extracting in the residue of preparing alcohol fuel by fermentation of plant straws.At present; most enzymolysis xylogen is for burning; not only its composition is not utilized effectively; and contaminate environment; China produces 6,700,000,000 tons of maize straws now per year, and the residue that alcohol fuel is prepared in every 1 ton of maize straw fermentation can obtain the xylogen of 300 kilograms of left and right, the resource rational utilization that therefore efficiently utilizes enzymolysis xylogen not only can do; again can petroleum replacing Chemicals, protection of the environment.In the present invention, xylogen used derives from the residue that the agricultural wastes such as corn cob, maize straw are produced alcohol fuel or butanols.
By phenolic compound and aldehyde compound, under catalyst action, polycondensation forms resol.Resol is because cheap, heat-resisting, resistance to ablation, fire-retardant, burning fuming is few etc. is widely used in sizing agent, coating, moulding compound, stratified plastics, porous plastics and ion exchange resin etc.The production of resol and the meeting of use consume bulk petroleum Chemicals, and bring pollution to a certain degree to environment, affect the whole ecosystem.For the production of the phenol of the main petrochemicals of resol,, the price of formaldehyde improves constantly, cause China's resol relevant industries profit sharply to decline, have a strong impact on the development of resol industry.
Cheng Xian Sue, Zheng Zhifeng etc. adopt the strong acid as catalyst such as the vitriol oil, hydrochloric acid, and phenol is made liquefying agent liquefied wood quality, not only to environment, and also serious to equipment corrosion, adopt the organic monoacids such as oxalic acid not good enough as the catalytic effect of catalyzer.Therefore research and develop new catalyst for efficiently utilizing natural biomass resource to there is particularly important meaning.Used catalyst heteropolyacid of the present invention is a kind of catalyzer of environmental protection, and not only catalytic effect is more desirable than weak acid, and has solved vitriol oil etc. to the highly corrosive of equipment and the pollution problem to environment.
Summary of the invention
The object of this invention is to provide a kind of environmental protection, good combination property, the liquefying lignin method for the preparation of resol that yield is higher, preparation method is simple, effectively utilized the residue that biomass fuel ethanol or butanols preparation process produce, and the heteropolyacid that adopts environmental protection substitutes corrosive acid as catalyzer, novolac resin environmental protection, the cost with the liquefying lignin product in the present invention, prepared are low, free phenol content is low.
The present invention adopts following technical scheme: a kind of liquefying lignin method for the preparation of novolac resin: phenol, acid catalyst and enzymolysis xylogen are mixed, by changing the add-on of acid catalyst, regulate the Ph value of above-mentioned reaction system to 1-3, reheat 90 ℃-160 ℃, reaction 1-3h, obtains enzymolysis xylogen liquefied product.
Described enzymolysis xylogen is for preparing bio-ethanol or biological butanol by product enzymolysis xylogen.
Described acid catalyst is one or more in phospho-wolframic acid, silicotungstic acid.
Described acid catalyst consumption is the 0.5%-4% of phenol quality.
The mass ratio of enzymolysis xylogen and phenol is 10-60:100.
Invention effect:
1. because energy problem is becoming tight day, the research and development of biofuel ethanol or butanols are promoted and are come into one's own, and therefore effectively utilize enzymolysis xylogen, can reduce the cost of biofuel enterprise, promote the development of China's biofuel cause.
2. the present invention be take phenol as liquefying agent, and gained liquefied product can be directly used in the synthetic of novolac resin.
3. the heteropolyacid that catalyzer of the present invention is environmental protection, can solve the not good problem of weak acid catalytic effect, can solve the etching problem that strong acid brings to equipment again.
4. in the present invention, the residue rate of liquefying lignin is 0.5-20%, lower than general weak acid catalyzed residue rate.
5. in the present invention, in liquefied product, the yield of phenolic compound is 40-70%, higher than general weak acid catalyzed liquefied product.
6. in the present invention, lignin phenol liquefied product molecular weight reduces, and dispersion coefficient (Mw/Mn) reduces 50-90%, and liquefied residue molecular weight is 1100-2300, containing phenol structural content, increase, with respect to xylogen macromole, it is high that it has reactive behavior, speed of response is fast, the feature that production efficiency is high.
7. the liquefied product of gained of the present invention can substitute phenol for the preparation of novolac resin, substitution rate >50%, and also the resol making has low cost, the feature of hypotoxicity (reduction of free phenol content).
Accompanying drawing explanation
The gpc chromatogram of Fig. 1 embodiment 2 enzymolysis xylogen raw materials.
The gpc chromatogram of Fig. 2 embodiment 2 catalysis of phosphotungstic acid liquefaction enzymolysis lignin residue.
From Fig. 1,2, can find out, through the molecular weight of the enzymolysis xylogen after catalysis of phosphotungstic acid liquefaction, obviously reduce, and dispersion coefficient also decreases, this explanation enzymolysis xylogen macromole is transformed into the micromolecular compound that is more conducive in a large number resin reaction.
Embodiment
Embodiment 1
A liquefying lignin method for novolac resin, liquifying method is as follows: phenol, heteropolyacid catalyst and enzymolysis xylogen are mixed, be heated to 90 ℃-160 ℃, reaction 1-3h.Wherein, the mass ratio of acid catalyst and phenol is 0.5-4:100, and the mass ratio of xylogen and phenol is 10-60:100, liquefied residue rate is 0.5-20%, the yield of phenolic compound is 40-70%, and liquefied residue molecular weight is 1100-2300, and dispersion coefficient (Mw/Mn) reduces 50-90%.The xylogen of participating in this reaction is enzymolysis xylogen, and this xylogen can extract and obtain from the residue of the plant material biorefinery (biofuel ethanol or butanols) that contains Mierocrystalline cellulose, hemicellulose.
Embodiment 2
A certain amount of phenol, enzymolysis xylogen (account for phenol quality 33%) and phospho-wolframic acid (account for phenol quality 0.5%) are added in reactor, 95 ℃ of temperature of reaction, reaction times 2h, make enzymolysis xylogen liquefied product, residue rate is 11.5%, the yield of phenolic compound is 47%, and liquefied residue molecular weight is 1910.
Embodiment 3
A certain amount of phenol, enzymolysis xylogen (phenol quality 33%) and phospho-wolframic acid (phenol quality 1%) are added in reactor, 115 ℃ of temperature of reaction, reaction times 1.5h, make enzymolysis xylogen liquefied product, residue rate is 9.7%, the yield of phenolic compound is 56%, and liquefied residue molecular weight is 1790.
Embodiment 4
A certain amount of phenol, enzymolysis xylogen (account for phenol quality 33%) and phospho-wolframic acid (account for phenol quality 2%) are added in reactor, 135 ℃ of temperature of reaction, reaction times 2h, make enzymolysis xylogen liquefied product, residue rate is 1.6%, the yield of phenolic compound is 63%, and liquefied residue molecular weight is 1380.
Embodiment 5
A certain amount of phenol, enzymolysis xylogen (account for phenol quality 50%) and phospho-wolframic acid (account for phenol quality 2%) are added in reactor, 135 ℃ of temperature of reaction, reaction times 2h, make enzymolysis xylogen liquefied product, residue rate is 6.3%, the yield of phenolic compound is 61%, and liquefied residue molecular weight is 1420.
Embodiment 6
A certain amount of phenol, enzymolysis xylogen (account for phenol quality 33%) and silicotungstic acid (account for phenol quality 2%) are added in reactor, 135 ℃ of temperature of reaction, reaction times 2h, make enzymolysis xylogen liquefied product, residue rate is 2.6%, the yield of phenolic compound is 53%, and liquefied residue molecular weight is 1880.
Embodiment 7
A certain amount of phenol, enzymolysis xylogen (account for phenol quality 33%) and phospho-wolframic acid, silicotungstic acid 1:1 mixture (account for phenol quality 2%) are added in reactor, 135 ℃ of temperature of reaction, reaction times 2h, make enzymolysis xylogen liquefied product, residue rate is 2.1%, the yield of phenolic compound is 58%, and liquefied residue molecular weight is 1590.
Comparative example 1
A certain amount of phenol, enzymolysis xylogen (account for phenol quality 33%) and Catalyzed by p-Toluenesulfonic Acid agent (account for phenol quality 1%) are added in reactor, 135 ℃ of temperature of reaction, reaction times 2h, residue rate is 21%, the yield of phenolic compound is 49%, liquefied residue molecular weight is 2130, and liquefaction effect is not good enough.
Comparative example 2
A certain amount of phenol, enzymolysis xylogen (account for phenol quality 33%) and Catalyzed by Oxalic Acid agent (phenol quality 1%) are added in reactor, 135 ℃ of temperature of reaction, reaction times 2h, residue rate is 35%, the yield of phenolic compound is 44%, liquefied residue molecular weight is 1750, and liquefaction effect is not good enough.
Comparative example 3
A certain amount of phenol, enzymolysis xylogen (account for phenol quality 33%) and acetic acid (account for phenol quality 1%) are added in reactor, 135 ℃ of temperature of reaction, reaction times 2h, residue rate is 89%, the yield of phenolic compound is 32%, liquefied residue molecular weight is 4760, almost there is no liquefaction effect.
Comparative example 4
A certain amount of phenol, enzymolysis xylogen (account for phenol quality 33%) and sulfocarbolic acid (phenol quality 1%) are added in reactor to 135 ℃ of temperature of reaction, reaction times 2h, residue rate is 83%, the yield of phenolic compound is 36%, and liquefied residue molecular weight is 4230, liquefaction effect extreme difference.
Note: the national standard of each index reference
The mensuration of HG/T2753-1996 resol mobile distance on sheet glass
HG5-1338-80 resol polymerization velocity experimental technique
GB/T8146-2003 Test methods of rosin (softening temperature).
Claims (5)
1. for the preparation of a liquefying lignin method for novolac resin, it is characterized in that, phenol, acid catalyst and enzymolysis xylogen are mixed, be heated to 90 ℃-160 ℃, reaction 1-3h, to resin, splashing in water is terminal without diffusion and hangover;
Wherein, acid catalyst used is one or more mixtures in heteropolyacid phospho-wolframic acid, silicotungstic acid.
2. the liquefying lignin method for the preparation of novolac resin according to claim 1, is characterized in that: enzymolysis xylogen used is the by product enzymolysis xylogen of preparing bio-ethanol or biological butanol.
3. the liquefying lignin method for the preparation of novolac resin according to claim 1, is characterized in that: liquefying agent used is phenol.
4. the liquefying lignin method for the preparation of novolac resin according to claim 1, is characterized in that: the quality of described acid catalyst is the 0.5%-4% of phenol quality.
5. the liquefying lignin method for the preparation of novolac resin according to claim 1, is characterized in that: described enzymolysis xylogen and the mass ratio of phenol are 10-60:100.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105754059A (en) * | 2016-05-18 | 2016-07-13 | 浙江大学 | Thermoplastic phenolic resin synthesized by liquefied bamboo waste as well as preparation method and application of thermoplastic phenolic resin |
| CN106046393A (en) * | 2016-07-15 | 2016-10-26 | 安吉威龙塑木环保材料有限公司 | Bamboo liquefying method |
| CN106380887A (en) * | 2016-09-27 | 2017-02-08 | 中国林业科学研究院林产化学工业研究所 | Preparation method of lignin-base phenolic aldehyde molding compound |
| CN110891960A (en) * | 2017-08-10 | 2020-03-17 | 出光兴产株式会社 | Method for producing modified lignin and modified polyphenol, and resin composition material using modified lignin |
| CN110914341A (en) * | 2017-08-10 | 2020-03-24 | 出光兴产株式会社 | Method for producing modified lignin, and resin composition material containing modified lignin |
| CN112143246A (en) * | 2020-09-19 | 2020-12-29 | 周静 | Application method of lignin in phenolic resin molding compound |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
Non-Patent Citations (1)
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| 牟莉等: "常规加热条件下四种不同强度酸对玉米秸秆降解的影响", 《长春大学学报》, vol. 18, no. 6, 31 December 2008 (2008-12-31), pages 42 - 45 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105754059A (en) * | 2016-05-18 | 2016-07-13 | 浙江大学 | Thermoplastic phenolic resin synthesized by liquefied bamboo waste as well as preparation method and application of thermoplastic phenolic resin |
| CN105754059B (en) * | 2016-05-18 | 2018-05-04 | 浙江大学 | A kind of thermoplastic phenolic resin synthesized by bamboo wood scrap material liquefied substance and preparation method and application |
| CN106046393A (en) * | 2016-07-15 | 2016-10-26 | 安吉威龙塑木环保材料有限公司 | Bamboo liquefying method |
| CN106380887A (en) * | 2016-09-27 | 2017-02-08 | 中国林业科学研究院林产化学工业研究所 | Preparation method of lignin-base phenolic aldehyde molding compound |
| CN110891960A (en) * | 2017-08-10 | 2020-03-17 | 出光兴产株式会社 | Method for producing modified lignin and modified polyphenol, and resin composition material using modified lignin |
| CN110914341A (en) * | 2017-08-10 | 2020-03-24 | 出光兴产株式会社 | Method for producing modified lignin, and resin composition material containing modified lignin |
| US11505655B2 (en) | 2017-08-10 | 2022-11-22 | Idemitsu Kosan Co., Ltd. | Modified lignin manufacturing method, modified lignin, and modified lignin-including resin composition material |
| US11518886B2 (en) | 2017-08-10 | 2022-12-06 | Idemitsu Kosan Co., Ltd. | Modified lignin, modified polyphenol manufacturing method, and modified lignin-including resin composition material |
| CN110914341B (en) * | 2017-08-10 | 2023-02-21 | 出光兴产株式会社 | Method for producing modified lignin, and resin composition material containing modified lignin |
| CN112143246A (en) * | 2020-09-19 | 2020-12-29 | 周静 | Application method of lignin in phenolic resin molding compound |
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Application publication date: 20140205 |