CN107629180A - A kind of preparation method of calcium precipitation lignin-base phenolic resin - Google Patents
A kind of preparation method of calcium precipitation lignin-base phenolic resin Download PDFInfo
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- CN107629180A CN107629180A CN201610565921.1A CN201610565921A CN107629180A CN 107629180 A CN107629180 A CN 107629180A CN 201610565921 A CN201610565921 A CN 201610565921A CN 107629180 A CN107629180 A CN 107629180A
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- lignin
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Abstract
A kind of preparation method of calcium precipitation lignin-base phenolic resin, it is related to a kind of method with calcium precipitation lignin, and then the method for part phenol synthesis phenolic resin is substituted using calcium precipitation lignin.The present invention is with enzymolysis xylogen, papermaking alkali lignin, furfural dregs etc. for raw material, with the method for alkali soluble by lignin dissolution in sig water, after filtering and impurity removing, lignin is precipitated out from black liquor using the complexing of calcium ion and lignin phenates, and with the phenol synthesis calcium precipitation lignin-base phenolic resin of calcium precipitation lignin substitution 20%~70%.The rate of recovery of lignin is up to the 80%, substitution rate of novolak resin phenol and can reach more than 50% in this method, and the bonding strength performance of phenolic resin remains to meet national standard, has broad application prospects.
Description
Technical field
Part phenol synthesis is substituted the present invention relates to one kind calcium precipitation lignin, and then using calcium precipitation lignin
The method of phenolic resin.
Background technology
Lignin is widely present in plant, winding is combined with cellulose hemicellulose reinforcing support is played to plant
Important function.Simultaneously as it belongs to the phenolic compound that reserves are maximum in nature, it can partly substitute and be provided from fossil
The phenol in source, the synthesis for phenolic resin.Therefore, with lignin modification phenolic resin, greenization, the height of phenolic resin are realized
Performance-based turns into researcher focus of attention.
At present, the report on lignin modification phenolic resin is more, but commercialized report is seldom, and this is mainly
Due to technique complexity and economy in terms of limitation.This method uses the technique of aqueous alkali dissolving, then uses calcium precipitation
Method recovery lignin, alkali collection liquid can recycle again, so as to realize recycling for resource.Calcium precipitation is wooden
Element, lignin is precipitated out from alkali lye using the complexing of calcium ion and lignin phenates, not to the knot of lignin
It is configured to destroy, while reduces the use of acid, substantially reduces the corrosion of equipment, it is cost-effective.
The content of the invention
The invention provides one kind calcium precipitation lignin, and then substitute part phenol using calcium precipitation lignin and close
Into the method for phenolic resin, to solve the problems, such as lignin separation and utilize.
In the present invention, the preparation of calcium precipitation lignin-base phenolic resin, specifically carry out in the steps below：First, will
A certain amount of lignin raw material and aqueous alkali are placed in the there-necked flask with agitator, are sufficiently stirred at a certain temperature, filtering
Insoluble matter is removed, collects lignin extraction liquid；2nd, to lignin extraction liquid in add soluble calcium salt, be sufficiently stirred, be quiet
Put, filter, filter cake is calcium precipitation lignin, and supernatant can be reclaimed for calcium precipitation lignin extraction liquid next time；
3rd, phenol, a certain amount of calcium precipitation lignin, 1/3 sodium hydrate aqueous solution and ethanol in proper amount are added in there-necked flask fully
Stirring, then add 1/3 formaldehyde, in 80 DEG C or back flow reaction 1h；Add 1/3 formaldehyde and 1/3 sodium hydroxide, continue
In 80 DEG C or back flow reaction 1h；Add last 1/3 formaldehyde and 1/3 sodium hydroxide in 80 DEG C or back flow reaction 30~
60min；4th, part second alcohol and water is distilled to recover in 30min, product solid content is reached more than 35%, by reactant
System is quickly cooled to less than 40 DEG C.
Raw material wood element is carried out in extraction process described in step 1, lignin raw material is enzymolysis xylogen, papermaking alkali
One or more of mixtures in lignin, furfural dregs, dilute alkaline aqueous solution are that hydroxyl radical negative ion molar concentration is 10-2~
One kind or mixture in 4mol/L sodium hydrate aqueous solution or potassium hydroxide aqueous solution, the dosage of aqueous alkali is lignin
5~40 times of material quality, temperature is 10~90 DEG C when mixing, stirring with lignin, and mixing time is 10~120min.Use calcium
Lignin in salt precipitation extract solution, the soluble calcium salt added is calcium chloride or one kind or mixture in calcium sulfate, calcium from
Son is 10 relative to the dosage of lignin extraction thing mixed liquor-2~2mol/L, temperature be 10~90 DEG C, mixing time be 3~
30min, it is 2~20h to staticly settle the time.Phenol described in step 3, formaldehyde mole ratio 1:1.5~1:4.0, over dry calcium salt
The substitution rate of precipitate lignin Pyrogentisinic Acid is 20%~70%, and sodium hydroxide total addition level is calcium precipitation lignin and phenol matter
The 5~20% of amount, ethanol consumption are 1/5~5 times of formalin volumetric usage.In step 4 be distilled to recover part ethanol and
Water, product solid content is reached more than 35%, reaction system is quickly cooled to less than 40 DEG C.
The present invention extracts lignin from the material rich in lignin first, the precipitation using soluble calcium salt as lignin
Agent, lignin is set to be separated with other impurity, for partly substituting phenol synthesis calcium precipitation lignin-base phenolic resin.The present invention
In under optimum condition lignin the rate of recovery up to 80%, the substitution rate of Pyrogentisinic Acid is up to more than 50% in phenolic resin synthesis
When, indices still are able to the requirement being up to state standards.
The present invention is simple to the processing procedure of lignin, and effect is very notable, environment-friendly, meets wanting for Green Chemistry
Ask.
Embodiment
Embodiment 1：
Paper industry alkali lignin 500g is taken, is sufficiently stirred with 0.05mol/L sodium hydrate aqueous solution 10L at 40 DEG C
50min, insoluble impurity is filtered to remove, collects filtrate and add 50g calcium chloride thereto, be sufficiently stirred, stand, filter, collect
Filter cake is calcium precipitation lignin, and measure wherein moisture content is 92%.18g phenol and 180g calcium precipitations lignin is taken to stir
Mixing (is 0.8 with phenol quality ratio:1) it is sufficiently stirred at room temperature after, adding sodium hydroxide 1.8g, it is molten adds 16mL formaldehyde
Liquid (37%) simultaneously promotes whole system mixing more uniform with 30mL ethanol, and in 80 DEG C of heating water baths, condensing reflux adds per 1h
16mL formalins (37%) and sodium hydroxide 1.8g, stop reaction after the 2.5h that flows back, steam ethanol and aqueous solvent and amount to about
50g, 40 DEG C are finally rapidly cooled to bottom discharge.After obtaining calcium precipitation lignin-base phenolic resin pressing plate, the glue of glued board
It is respectively 1.16MPa and 1.27MPa to close wet strength and dry strength.
Embodiment 2：
Furfural dregs 500g is taken, 90min is sufficiently stirred at 80 DEG C with 0.5mol/L sodium hydrate aqueous solution 10L, crosses and filters out
Insoluble impurity is removed, filtrate is collected and adds 37g calcium chloride thereto, be sufficiently stirred, stand, filter, it is calcium salt to collect filter cake
Precipitate lignin, measure wherein moisture content are 86%.18g phenol and 130g lignin calcium salts is taken to be stirred (with phenol quality
Than for 1:1) it is sufficiently stirred at room temperature after, adding sodium hydroxide 2.4g, adds 15mL formalins (37%) and use 30mL
Ethanol promotes whole system mixing more uniform, in 80 DEG C of heating water baths, condensing reflux addition 15mL formalins per 1h
(37%) and after sodium hydroxide 2.4g, the 3h that flows back stop reaction, steam ethanol and aqueous solvent amounts to about 40g, last rapid cooling
To 40 DEG C with bottom discharge.After obtaining calcium precipitation lignin-base phenolic resin pressing plate, the glued wet strength and dry strength of glued board
Respectively 1.16MPa and 1.27MPa.
Claims (7)
1. the preparation method of calcium precipitation lignin-base phenolic resin, it comprises the concrete steps that and carried out in the steps below：First, will be certain
Amount lignin raw material and aqueous alkali are placed in the there-necked flask with agitator, are sufficiently stirred, are filtered to remove at a certain temperature
Insoluble matter, collect lignin extraction liquid；2nd, to lignin extraction liquid in add soluble calcium salt, be sufficiently stirred, stand, take out
Filter, filter cake are calcium precipitation lignin, and supernatant can be reclaimed for calcium precipitation lignin extraction liquid next time；3rd, will
Phenol, a certain amount of calcium precipitation lignin, 1/3 sodium hydrate aqueous solution and ethanol in proper amount are added in there-necked flask and are sufficiently stirred,
Then 1/3 formaldehyde is added, in 80 DEG C or back flow reaction 1h；Add 1/3 formaldehyde and 1/3 sodium hydroxide, continue at 80
DEG C or back flow reaction 1h；1/3 last formaldehyde and 1/3 sodium hydroxide are added in 80 DEG C or 30~60min of back flow reaction；
4th, part second alcohol and water is distilled to recover in 30min, product solid content is reached more than 35%, reaction system is quick
It is cooled to less than 40 DEG C.
2. the preparation of calcium precipitation lignin-base phenolic resin according to claim 1, it is characterised in that lignin used
Raw material is one or more of mixtures in enzymolysis xylogen, papermaking alkali lignin, furfural dregs.
3. the preparation of calcium precipitation lignin-base phenolic resin according to claim 1, it is characterised in that made in step 1
Aqueous alkali used is sodium hydrate aqueous solution or one kind or mixture in potassium hydroxide aqueous solution during standby lignin extraction liquid.
4. the preparation of calcium precipitation lignin-base phenolic resin according to claim 3, it is characterised in that made in step 1
The hydroxyl radical negative ion molar concentration of aqueous alkali used is 10 during standby lignin extraction liquid-2~4mol/L, the use of aqueous alkali
Measure as 5~40 times of lignin material quality, when mixing, stirring with lignin temperature be 10~90 DEG C, mixing time be 10~
120min。
5. the preparation of calcium precipitation lignin-base phenolic resin according to claim 1, it is characterised in that in step 2 to
The soluble calcium salt added in lignin extraction liquid is calcium chloride or one kind or mixture in calcium sulfate.
6. the preparation of calcium precipitation lignin-base phenolic resin according to claim 5, it is characterised in that carried to lignin
When taking addition calcium salt in liquid, calcium ion is 10 relative to the dosage of lignin extraction thing mixed liquor-2~2mol/L, temperature be 10~
90 DEG C, mixing time is 3~30min, and it is 2~20h to staticly settle the time.
7. the preparation of calcium precipitation lignin-base phenolic resin according to claim 1, it is characterised in that institute in step 3
State phenol, formaldehyde mole ratio 1:1.5~1:4.0, the substitution rate of over dry calcium precipitation lignin Pyrogentisinic Acid is 20%~70%,
Sodium hydroxide total addition level is the 5~20% of calcium precipitation lignin and phenol quality sum, and ethanol consumption is formalin
1/5~5 times of volumetric usage.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610565921.1A CN107629180A (en) | 2016-07-19 | 2016-07-19 | A kind of preparation method of calcium precipitation lignin-base phenolic resin |
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| CN201610565921.1A CN107629180A (en) | 2016-07-19 | 2016-07-19 | A kind of preparation method of calcium precipitation lignin-base phenolic resin |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256824A (en) * | 2019-07-02 | 2019-09-20 | 南京工业大学 | A kind of complete biodegradable film and preparation method thereof that lignin calcium is compound |
| CN114369435A (en) * | 2022-02-21 | 2022-04-19 | 石河子大学 | Preparation method of biomass-based adhesive and adhesive |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101023215A (en) * | 2004-07-09 | 2007-08-22 | 基米勒公司 | Method for removing lignin from water |
| CN104140508A (en) * | 2013-05-09 | 2014-11-12 | 东北林业大学 | Preparation method of enzymolysis lignin-based phenolic resin |
| CN104250361A (en) * | 2013-06-26 | 2014-12-31 | 中国科学院化学研究所 | Lignin modified phenolic resin, foam thereof, preparation method of resin, and preparation method of foam |
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2016
- 2016-07-19 CN CN201610565921.1A patent/CN107629180A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101023215A (en) * | 2004-07-09 | 2007-08-22 | 基米勒公司 | Method for removing lignin from water |
| CN104140508A (en) * | 2013-05-09 | 2014-11-12 | 东北林业大学 | Preparation method of enzymolysis lignin-based phenolic resin |
| CN104250361A (en) * | 2013-06-26 | 2014-12-31 | 中国科学院化学研究所 | Lignin modified phenolic resin, foam thereof, preparation method of resin, and preparation method of foam |
Non-Patent Citations (1)
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| 方强等: "絮凝法分离稻草秸秆预处理碱液中的木质素", 《化工进展》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256824A (en) * | 2019-07-02 | 2019-09-20 | 南京工业大学 | A kind of complete biodegradable film and preparation method thereof that lignin calcium is compound |
| CN114369435A (en) * | 2022-02-21 | 2022-04-19 | 石河子大学 | Preparation method of biomass-based adhesive and adhesive |
| CN114369435B (en) * | 2022-02-21 | 2023-10-13 | 石河子大学 | Preparation method of biomass-based adhesive and adhesive |
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