CN106810653A - A kind of method of biorefinery Bagasse Lignin base phenolic resin and its application - Google Patents
A kind of method of biorefinery Bagasse Lignin base phenolic resin and its application Download PDFInfo
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- CN106810653A CN106810653A CN201710058054.7A CN201710058054A CN106810653A CN 106810653 A CN106810653 A CN 106810653A CN 201710058054 A CN201710058054 A CN 201710058054A CN 106810653 A CN106810653 A CN 106810653A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with monohydric phenols having only one hydrocarbon substituent ortho on para to the OH group, e.g. p-tert.-butyl phenol
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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Abstract
The invention discloses a kind of method of biorefinery Bagasse Lignin base phenolic resin, comprise the following steps：(1) catalytic degradation of lignin：The single phenolic compound of microwave assistant lignin directional catalyzing degraded；(2) purifying of catabolite：Low temperature is rotated, and removes reaction dissolvent；(3) preparation of phenolic resin：Catabolite part replaces phenol, and phenolic resin is prepared with formaldehyde reaction.The preparation method of relatively conventional lignin base phenolic resin, the present invention assembles heteropoly acid saline catalyst by unique fluorinated graphene, can efficiently, high selectivity catalysis lignin for high reaction activity 4 ethyl -phenols, simultaneously, the catalyst can also be catalyzed the condensation reaction of both lignin degradation product, phenol between formaldehyde and prepare lignin base phenolic resin, the step of saving the separation of catalyst and extra addition catalyst, this method have efficiently, low cost and the characteristics of strong applicability.
Description
【Technical field】
The present invention relates to Industrial Catalysis and polymeric material field, more particularly to a kind of biorefinery Bagasse Lignin base phenolic aldehyde
The method of resin.
【Background technology】
Bagasse Lignin is by multiple phenylpropyl alcohol alkyl structure units (mainly guaiacyl structure, lilac based structures and to hydroxyl
Phenyl structure) composition a kind of complicated phenol polymer, be a kind of biological refining the features such as with renewable, neutral carbon, low stain
The raw material of the high-quality of system；With the increasingly reduction of fossil energy, with Wooden Biomass such as Bagasse Lignins as raw material, refined by biology
The method of system obtains the energy, fuels and chemicals becomes most important.With to the distinctive monocyclic aromatic rings primitive structure of lignin and
The development fully realized with associated catalytic science and technology of chemical characteristic, is degraded/is split by conversion technology and chemical catalysis
Solution technology, can by the chemical intermediate that Bagasse Lignin is converted into various high activities be applied to for synthesize macromolecular material, dyestuff,
The fields such as the industry such as cement, ceramics, biomass energy and exploitation.
Phenolic resin be by phenol and formaldehyde under catalysts conditions polycondensation, neutralized, washing and the resin that is made.Phenolic aldehyde
Resin has good acid resistance, mechanical property, heat resistance, is widely used in moulding compound, casting, refractory material, friction
The fields such as material, grinding materials and grinding tool, oilfield additive, rubber for tire, composite, coating, adhesive.In recent years, along with state
The fast development of the industries such as interior automobile, metallurgy, consumer electronics, Aero-Space, the consumption figure of phenolic resin is in related application neck
To also keep the impetus of rapid growth, China's phenolic resin yield to improve rapidly in domain, counted according to national employer's organization, Chinese mesh
Family more than 100 of preceding phenolic resin manufacturing enterprise, production capacity more than 1,200,000 tons, 2011 annual China's phenolic resin yield
The 25.34% of the whole world has been accounted for, but because China's phenolic resin huge market demand, phenolic resin has serious market supply
Breach, annual import volume at 15~250,000 tons, under the general layout of current industrial rapid economic development, China's phenolic resin lack
Mouth will be widened further.Further, since one of raw material of phenolic resin phenol is a kind of chemical industry obtained from resources such as oil
Raw material, with the rise gradually decreased with oil price of petroleum resources, the price of phenol rise steadily (up to 8000~
11000 yuan/ton), the production cost of phenolic resin also increases sharply, the phenolic resin manufacturing enterprise of China because production scale compared with
Small, production technology falls behind, and product line is few, compared with external phenolic resin manufacturing enterprise, the phenolic resin production enterprise of China
The profit margin of industry receives more serious compression, therefore a kind of material that can partly substitute or substitute completely phenol of searching is compeled
In the eyebrows and eyelashes.Aromatic radical, phenolic hydroxyl group, alcoholic extract hydroxyl group, carbonyl, methoxyl group, carboxyl, conjugated double bond etc. are there is in the molecular structure of lignin
Active group, with certain reactivity.Particularly guaiacyl and p-hydroxyphenyl, similar to phenol structure, it is considered to be
Optimal phenol substitute.There is very strong reactivity their adjacent air space position, can under certain conditions participate in phenol, first
The condensation cured reaction of aldehyde, therefore can part fortified phenol, the production cost of reduction phenolic resin.
Phenol is substituted using lignin prepare the existing lot of documents report of phenolic resin, but because lignin is poly- phenols three dimensional network
Shape macromolecular compound, the connected mode between main structure body is mainly ehter bond and carbon-carbon bond, and both key molecular polarities are small, key
Can be high, steric hindrance is big on phenyl ring, and has been substituted avtive spot more, and no matter lignin reacts with phenol, formaldehyde, or and phenolic resin
Reaction, its reactivity is substantially not enough, and lignin is difficult to participate in the polycondensation reaction of phenol and formaldehyde, the substitution rate of lignin Pyrogentisinic Acid
It is low.Research finds that each lignin phenylpropyl alcohol alkane C9 construction units averagely only have 0.3 avtive spot can react with formaldehyde, and phenol
Having 3 avtive spots can react with formaldehyde.Because the reaction accessibility of lignin is relatively low, therefore lignin industrialized utilization is constantly subjected to
Limitation.By chemical modification, the methoxyl group on lignin aromatic ring is changed into phenolic hydroxyl group or methylolation, or make by degradation reaction
C-C keys and C-O keys between connection lignin phenylpropyl alcohol alkyl structure unit are broken, and are degraded to the phenolic compound of small molecule, make
It has the chemical active sites and solubility property close with phenol, makes lignin be expected to really be applied to phenol as phenol substitute
In the preparation of urea formaldehyde.
Fluorinated graphene be regarded as Graphene it is partially fluorinated or all fluorination result, it remains part Graphene
Sp2 structures and the Sp3 structures of itself.Fluorinated graphene is a kind of two-dimension plane structure, and wherein carbon atom and fluorine atom is with altogether
What the form of valence link was combined.As the new derivatives of Graphene, the performance of Graphene high intensity was both maintained, and because of fluorine atom
Introducing bring surface can reduce, hydrophobicity enhancing and the novel interface such as Bandgap extension and physical and chemical performance.Meanwhile, fluorine
Graphite alkene also has high temperature resistant, corrosion resistance, rub resistance, stable chemical nature and excellent lubricity, makes it in catalysis
The fields such as agent carrier, interface, novel nano electronic device, lubriation material are with a wide range of applications.At present, it is conventionally synthesized fluorine
The method of graphite alkene is using fluorization agents such as XeF2, to the Graphene peeled off using micromechanics or prepared by chemical vapor deposition
It is fluorinated.
Heteropoly acid is by certain by hetero atom (such as P, Si, Fe and Co) and polyatom (such as Mo, W, V, Nb and Ta)
The oxygen-containing polyacid of a class that structure is made up of oxygen atom ligand bridging, with catalysis activity very high, it not only has acidity, and
And be a kind of multifunctional novel catalyst with oxidation-reduction quality.Heteropoly acid good stability, can make homogeneous and heterogeneous anti-
Should, or even phase transfer catalyst can be made, and it is environmentally safe, it is the coming green catalyst of a class, can be used as with aromatic hydrocarbons
Alkylation and dealkylation, esterification, dehydration/combination reaction, redox reaction and open loop, condensation, addition and ether
Change reaction etc..
【The content of the invention】
In view of the problems during above-mentioned lignin base phenolic resin preparation, a kind of biological present invention aim at providing
The method for refining Bagasse Lignin base phenolic resin, heteropoly acid saline catalyst is assembled by unique fluorinated graphene, efficient, high
The catalysis lignin of selectivity is the 4- ethyl -phenols of high reaction activity, and the catalyst can also be catalyzed lignin degradation product, phenol
Both condensation reactions and between formaldehyde prepare lignin base phenolic resin, save the separation of catalyst and additionally add the third and urge
The step of agent, this method have efficiently, low cost and the characteristics of strong applicability.
To solve the above problems, the technical solution adopted in the present invention is：A kind of biorefinery Bagasse Lignin Ji Fenquanshu
The method of fat, comprises the following steps：
(1) catalytic degradation of lignin：Count by weight, by 10 parts of Bagasse Lignins, 100~300 parts of solvents and 0.01
~1 part of catalyst is added into microwave reactor, is stirred with the rotating speed of 300r/min, controls the power of microwave for 1000W,
Stop reaction, after natural cooling, the product after being degraded after reacting 20~60min at 180~250 DEG C；Described bagasse
Lignin is prepared with Klason acid precipitation methods, is specifically referred to by aqueous sulfuric acid that mass fraction is 72% to bagasse slurrying
Black liquor is neutralized, sediments of the step section pH produced by 2~3 of going forward side by side；
(2) purifying of catabolite：By the product after degraded in the bar that pressure is -0.09~-0.1MPa, temperature is 50 DEG C
3~5h of vacuum distillation under part, obtains product after purification；
(3) preparation of phenolic resin：During product after purification and phenol added into reactor, with turning for 400-500r/min
Speed stirring forms phenols mixed liquor, is heated to 80 DEG C, and formalin is added dropwise with the speed of 2mL/min, after completion of dropping, heats up
To 90~95 DEG C, 60~120min is reacted, cooling obtains final product sticky Bagasse Lignin base phenolic resin.
In the present invention, as further illustrating, the catalyst described in step (1) is fluorinated graphene and heteropolyacid salt
Assembling thing；The assembling thing of described fluorinated graphene and heteropolyacid salt is fluorinated graphene assembling Tricesium dodecatungstophosphate, fluorinated graphene
Assembling silicotungstic acid cesium, fluorinated graphene assembling phosphotungstic acid nickel and fluorinated graphene assembling silico-tungstic acid nickel in any one, preferably
Fluorinated graphene assembling Tricesium dodecatungstophosphate, fluorinated graphene assembling silicotungstic acid cesium.
In the present invention, as further illustrating, the weight ratio of fluorinated graphene and heteropolyacid salt in described catalyst
It is 7~9：1~3.
In the present invention, as further illustrating, the solvent described in step (1) is ethanol that mass fraction is 70~85%
The aqueous solution, mass fraction are 60~90% Isosorbide-5-Nitrae epoxy clustered water solution and methanol aqueous solution that mass fraction is 70~90%
In any one.Preferred mass fraction is 85% Isosorbide-5-Nitrae epoxy clustered water solution.
In the present invention, as further illustrating, the mass fraction of the formalin described in step (3) is 15~50%
Formalin.Preferred mass fraction is 40% formalin.
In the present invention, as further illustrating, product after purification, phenol and formalin described in step (3)
Weight ratio be 1~50：19~50：45~137.
The principle of realization of the invention：
Lignin is scattered in appropriate solvent, and selects suitable catalyst, can make connection lignin phenylpropyl alcohol alkyl structure unit it
Between C-C keys and C-O keys be broken, obtain various Small Phenolic Molecule compounds.But, due to connection Bagasse Lignin sugarcane fragrance
Methoxyl group bond energy is higher in ring structure unit, is difficult excision.The refining product of Bagasse Lignin mainly include 2- metoxyphenols, 2,
6- syringol, syringaldehyde；3- hydroxyls -4-methoxybenzaldehyde etc..These products are usual
The active group of only two or less than two, and participate in the phenyl ring 2,6 of condensation reaction and occupied by methoxyl group, or phenyl ring 3,
5 groups by big steric hindrance are occupied, and reactivity is not as good as pure phenol, and the reactivity with formaldehyde is poor.
Fluorinated graphene is that Graphene is partially fluorinated or result of all fluorinations, and it has high specific surface area, very thin
Thickness and smooth two-dimensional structure, can be used as excellent catalyst carrier or assembly.By fluorinated graphene and heteropolyacid salt
It is placed in water heating kettle, self assembly can slowly occurs under the high temperature conditions, by the quality for adjusting fluorinated graphene and heteropolyacid salt
Ratio, assembling temperature, solvent condition can obtain the high performance catalyst of variable acid strength, pore passage structure.Such catalyst is fitted
Single phenolic compound is prepared for lignin catalytic degraded, degraded selectivity is higher, and product is mainly 4- ethyl -phenols, relative to it
The common liquefaction products of lignin such as his 2- metoxyphenols, 2,6- syringol, because the virtue that it is participated in and formaldehyde contracting is reacted
2,6 side-chain radicals of fragrant ring are removed, and with reactivity higher, are particularly suited for the preparation of phenolic resin.
The invention has the advantages that：
(1) the fluorinated graphene assembling heteropoly acid saline catalyst that the present invention is used has two kinds of catalytic action, and one is high
Effect, high selectivity catalysis lignin degradation list phenolic compound, two can be both catalysis lignin degradation product, phenol between formaldehyde
Condensation reaction prepare lignin base phenolic resin.So save the separation of catalyst and additionally add the step of the third catalyst
Suddenly, production cost is reduced.
(2) main component of catabolite is 4- ethyl -phenols in the present invention, relative to other 2- metoxyphenols, 2,6-
The common catabolite of the lignins such as syringol, it is participated in and 2,6 side-chain radicals of aromatic rings of formaldehyde contracting reaction are removed,
With reactivity higher, phenolic resin high income；Meanwhile, the performance of the Bagasse Lignin base phenolic resin for preparing is more
Stabilization.
【Specific embodiment】
The present invention with gas chromatography mass spectrometry method, by Agilent 7200GC/Q-TOF HRGC-HRMS analysis-e/or determinings
The composition of phenolic compound, specific test condition is：HP-INNOWAX chromatographic columns are analyzed to liquefaction products；Wherein injection port
Temperature：220 DEG C, the μ L of sample size 5, split ratio 1/50；Carrier gas is high-purity helium, and flow velocity keeps 1mL/min；Heating schedule：50℃
2min is kept, 250 DEG C is warming up to the speed of 5 DEG C/min and is kept 2min；Solvent delay：3min.Mass spectrum ionization mode is EI；
Electron energy is 70ev；250 DEG C of ion source temperature, 150 DEG C of level Four bar temperature, charge-mass ratio sweep limits：0~1000amu, experiment
Result is qualitative according to NIST11 databases.
The degradation rate and 4- ethyl -phenols yield of lignin are calculated according to below equation：
4- ethyl -phenols yield (%)=4- ethyl -phenols weight/lignin addition × 100%
Bagasse Lignin base phenolic resin is pre-processed into (the small molecule thing such as removal formaldehyde, water in 95 DEG C of Rotary Evaporators
Matter), the Bagasse Lignin base phenolic resin of solid-like is obtained after cooling.After being dissolved with DMF, using the gels of Waters 1515/2414
Permeation chromatograph determines Bagasse Lignin base phenolic resin molecular weight and molecualr weight distribution, and test column temperature is kept for 40 DEG C, and flow velocity is
1mL/min polystyrene is standard specimen.
The viscosity of Bagasse Lignin base phenolic resin uses the NDJ-9S digital display viscosity of Shanghai Precision Scientific Apparatus Co., Ltd
Meter is determined, during about 40mL samples are placed in into a diameter of 30mm, volume 50mL sample cells, after constant temperature 30min in 25 DEG C of water-baths, and choosing
Select suitable rotor and be dipped vertically into sample centre, viscosity, each sample balancing side three times are determined with 30r/min rotating speeds.
Embodiment 1：
A kind of method of biorefinery Bagasse Lignin base phenolic resin, comprises the following steps：
(1) catalytic degradation of lignin：Count by weight, by the second that 10 parts of Bagasse Lignins, 100 parts of mass fractions are 70%
Alcohol solution and 0.01 part of fluorinated graphene assembling Tricesium dodecatungstophosphate are added into microwave reactor, wherein fluorinated graphene and phosphorus
The weight ratio of wolframic acid caesium is 7：1, then stirred with the rotating speed of 300r/min, the power of microwave is controlled for 1000W, 180
Stop reaction, after natural cooling, the product after being degraded after 20min is reacted at DEG C；
(2) purifying of catabolite：By the product after degraded pressure be -0.09MPa, temperature be 50 DEG C under conditions of subtract
Pressure distillation 3h, obtains product after purification；
(3) preparation of phenolic resin：Count by weight, 1 part of product and 19 parts of phenol after purification is added into reactor
In, stir to form phenols mixed liquor with the rotating speed of 400r/min, it is heated to DEG C, 45 parts of quality point are added dropwise with the speed of 2mL/min
Number is 40% formalin, after completion of dropping, is warming up to 90 DEG C, reacts 60min, and cooling obtains final product sticky Bagasse Lignin base
Phenolic resin.
Embodiment 2：
A kind of method of biorefinery Bagasse Lignin base phenolic resin, comprises the following steps：
(1) catalytic degradation of lignin：Count by weight, by the second that 10 parts of Bagasse Lignins, 300 parts of mass fractions are 75%
Alcohol solution and 0.08 part of fluorinated graphene assembling Tricesium dodecatungstophosphate are added into microwave reactor, wherein fluorinated graphene and phosphorus
The weight ratio of wolframic acid caesium is 8：1.5, then stirred with the rotating speed of 300r/min, the power of microwave is controlled for 1000W,
Stop reaction, after natural cooling, the product after being degraded after 35min is reacted at 200 DEG C；
(2) purifying of catabolite：By the product after degraded pressure be -0.095MPa, temperature be 50 DEG C under conditions of
Vacuum distillation 3.5h, obtains product after purification；
(3) preparation of phenolic resin：Count by weight, 20 parts of products and 40 parts of phenol after purification are added into reactor
In, stir to form phenols mixed liquor with the rotating speed of 430r/min, 80 DEG C are heated to, 100 parts of quality are added dropwise with the speed of 2mL/min
Fraction is 15% formalin, after completion of dropping, is warming up to 92 DEG C, reacts 85min, and cooling obtains final product sticky Bagasse Lignin
Base phenolic resin.
Embodiment 3：
A kind of method of biorefinery Bagasse Lignin base phenolic resin, comprises the following steps：
(1) catalytic degradation of lignin：Count by weight, by the second that 10 parts of Bagasse Lignins, 250 parts of mass fractions are 85%
Alcohol solution and 0.3 part of fluorinated graphene assembling Tricesium dodecatungstophosphate are added into microwave reactor, wherein fluorinated graphene with it is miscellaneous
The weight ratio of multi-acid salt is 3：1, then stirred with the rotating speed of 300r/min, the power of microwave is controlled for 1000W, 250
Stop reaction, after natural cooling, the product after being degraded after 60min is reacted at DEG C；
(2) purifying of catabolite：By the product after degraded pressure be -0.094MPa, temperature be 50 DEG C under conditions of
Vacuum distillation 4h, obtains product after purification；
(3) preparation of phenolic resin：Count by weight, 30 parts of products and 45 parts of phenol after purification are added into reactor
In, stir to form phenols mixed liquor with the rotating speed of 420r/min, 80 DEG C are heated to, 60 parts of quality are added dropwise with the speed of 2mL/min
Fraction is 30% formalin, after completion of dropping, is warming up to 93 DEG C, reacts 100min, and cooling obtains final product sticky bagasse wood
Plain base phenolic resin.
Embodiment 4：
A kind of method of biorefinery Bagasse Lignin base phenolic resin, comprises the following steps：
(1) catalytic degradation of lignin：Count by weight, by 10 parts of Bagasse Lignins, 120 parts of mass fractions are 85% 1,
4 epoxy clustered water solution and 0.3 part of fluorinated graphene assembling silicotungstic acid cesium are added into microwave reactor, wherein fluorographite
Alkene is 7.5 with the weight ratio of silicotungstic acid cesium：1.4, then stirred with the rotating speed of 300r/min, the power for controlling microwave is
1000W, reaction, after natural cooling, the product after being degraded are stopped after reacting 28min at 190 DEG C；
(2) purifying of catabolite：By the product after degraded pressure be -0.093MPa, temperature be 50 DEG C under conditions of
Vacuum distillation 4h, obtains product after purification；
(3) preparation of phenolic resin：Count by weight, 20 parts of products and 42 parts of phenol after purification are added into reactor
In, stir to form phenols mixed liquor with the rotating speed of 415r/min, 80 DEG C are heated to, 60 parts of quality are added dropwise with the speed of 2mL/min
Fraction is 36% formalin, after completion of dropping, is warming up to 91 DEG C, reacts 100min, and cooling obtains final product sticky bagasse wood
Plain base phenolic resin.
Embodiment 5：
A kind of method of biorefinery Bagasse Lignin base phenolic resin, comprises the following steps：
(1) catalytic degradation of lignin：Count by weight, by 10 parts of Bagasse Lignins, 180 parts of mass fractions are 60% 1,
4 epoxy clustered water solution and 0.7 part of fluorinated graphene assembling silicotungstic acid cesium are added into microwave reactor, wherein fluorographite
Alkene is 8 with the weight ratio of silicotungstic acid cesium：3, then stirred with the rotating speed of 300r/min, the power of microwave is controlled for 1000W,
Stop reaction, after natural cooling, the product after being degraded after reacting 50min at 220 DEG C；
(2) purifying of catabolite：By the product after degraded pressure be -0.096MPa, temperature be 50 DEG C under conditions of
Vacuum distillation 4.5h, obtains product after purification；
(3) preparation of phenolic resin：Count by weight, 20 parts of products and 46 parts of phenol after purification are added into reactor
In, stir to form phenols mixed liquor with the rotating speed of 460r/min, 80 DEG C are heated to, 110 parts of quality are added dropwise with the speed of 2mL/min
Fraction is 47% formalin, after completion of dropping, is warming up to 93 DEG C, reacts 70min, and cooling obtains final product sticky Bagasse Lignin
Base phenolic resin.
Embodiment 6：
A kind of method of biorefinery Bagasse Lignin base phenolic resin, comprises the following steps：
(1) catalytic degradation of lignin：Count by weight, by 10 parts of Bagasse Lignins, 200 parts of mass fractions are 90% 1,
4 epoxy clustered water solution and 0.8 part of fluorinated graphene assembling silicotungstic acid cesium are added into microwave reactor, wherein fluorographite
Alkene is 9 with the weight ratio of silicotungstic acid cesium：2, then stirred with the rotating speed of 300r/min, the power of microwave is controlled for 1000W,
Stop reaction, after natural cooling, the product after being degraded after reacting 47min at 230 DEG C；
(2) purifying of catabolite：By the product after degraded pressure be -0.098MPa, temperature be 50 DEG C under conditions of
Vacuum distillation 4h, obtains product after purification；
(3) preparation of phenolic resin：Count by weight, 15 parts of products and 30 parts of phenol after purification are added into reactor
In, stir to form phenols mixed liquor with the rotating speed of 450r/min, 80 DEG C are heated to, 80 parts of quality are added dropwise with the speed of 2mL/min
Fraction is 36% formalin, after completion of dropping, is warming up to 92 DEG C, reacts 90min, and cooling obtains final product sticky Bagasse Lignin
Base phenolic resin.
Embodiment 7：
A kind of method of biorefinery Bagasse Lignin base phenolic resin, comprises the following steps：
(1) catalytic degradation of lignin：Count by weight, by the first that 10 parts of Bagasse Lignins, 150 parts of mass fractions are 70%
Alcohol solution and 0.1 part of fluorinated graphene assembling phosphotungstic acid nickel are added into microwave reactor, wherein fluorinated graphene and phosphorus
The weight ratio of nickel tungstate is 7：1.5, then stirred with the rotating speed of 300r/min, the power of microwave is controlled for 1000W,
Stop reaction, after natural cooling, the product after being degraded after 29min is reacted at 185 DEG C；
(2) purifying of catabolite：By the product after degraded pressure be -0.092MPa, temperature be 50 DEG C under conditions of
Vacuum distillation 3.5h, obtains product after purification；
(3) preparation of phenolic resin：Count by weight, 23 parts of products and 25 parts of phenol after purification are added into reactor
In, stir to form phenols mixed liquor with the rotating speed of 460r/min, 80 DEG C are heated to, 100 parts of quality are added dropwise with the speed of 2mL/min
Fraction is 25% formalin, after completion of dropping, is warming up to 94 DEG C, reacts 95min, and cooling obtains final product sticky Bagasse Lignin
Base phenolic resin.
Embodiment 8：
A kind of method of biorefinery Bagasse Lignin base phenolic resin, comprises the following steps：
(1) catalytic degradation of lignin：Count by weight, by the first that 10 parts of Bagasse Lignins, 220 parts of mass fractions are 82%
Alcohol solution and 0.3 part of fluorinated graphene assembling phosphotungstic acid nickel are added into microwave reactor, wherein fluorinated graphene and phosphorus
The weight ratio of nickel tungstate is 8.4：1.7, then stirred with the rotating speed of 300r/min, the power of microwave is controlled for 1000W,
Stop reaction, after natural cooling, the product after being degraded after 41min is reacted at 195 DEG C；
(2) purifying of catabolite：By the product after degraded pressure be -0.092MPa, temperature be 50 DEG C under conditions of
Vacuum distillation 3.5h, obtains product after purification；
(3) preparation of phenolic resin：Count by weight, 25 parts of products and 40 parts of phenol after purification are added into reactor
In, stir to form phenols mixed liquor with the rotating speed of 430r/min, 80 DEG C are heated to, 120 parts of quality are added dropwise with the speed of 2mL/min
Fraction is 30% formalin, after completion of dropping, is warming up to 91 DEG C, reacts 105min, and cooling obtains final product sticky bagasse wood
Plain base phenolic resin.
Embodiment 9：
A kind of method of biorefinery Bagasse Lignin base phenolic resin, comprises the following steps：
(1) catalytic degradation of lignin：Count by weight, by the first that 10 parts of Bagasse Lignins, 300 parts of mass fractions are 90%
Alcohol solution and 1 part of fluorinated graphene assembling phosphotungstic acid nickel are added into microwave reactor, wherein fluorinated graphene and phosphorus tungsten
The weight ratio of sour nickel is 9：2, then stirred with the rotating speed of 300r/min, the power of microwave is controlled for 1000W, at 196 DEG C
Stop reaction, after natural cooling, the product after being degraded after lower reaction 53min；
(2) purifying of catabolite：By the product after degraded pressure be -0.094MPa, temperature be 50 DEG C under conditions of
Vacuum distillation 4.5h, obtains product after purification；
(3) preparation of phenolic resin：Count by weight, 16 parts of products and 20 parts of phenol after purification are added into reactor
In, stir to form phenols mixed liquor with the rotating speed of 400-500r/min, 80 DEG C are heated to, it is added dropwise 70 parts with the speed of 2mL/min
Mass fraction is 50% formalin, after completion of dropping, is warming up to 90 DEG C, reacts 60~120min, and cooling obtains final product sticky
Bagasse Lignin base phenolic resin.
Embodiment 10：
A kind of method of biorefinery Bagasse Lignin base phenolic resin, comprises the following steps：
(1) catalytic degradation of lignin：Count by weight, by the second that 10 parts of Bagasse Lignins, 300 parts of mass fractions are 79%
Alcohol solution and 0.5 part of fluorinated graphene assembling silico-tungstic acid nickel are added into microwave reactor, wherein fluorinated graphene and silicon
The weight ratio of nickel tungstate is 8：3, then stirred with the rotating speed of 300r/min, the power of microwave is controlled for 1000W, 188
Stop reaction, after natural cooling, the product after being degraded after 47min is reacted at DEG C；
(2) purifying of catabolite：By the product after degraded pressure be -0.097MPa, temperature be 50 DEG C under conditions of
Vacuum distillation 5h, obtains product after purification；
(3) preparation of phenolic resin：Count by weight, 40 parts of products and 48 parts of phenol after purification are added into reactor
In, stir to form phenols mixed liquor with the rotating speed of 470r/min, 80 DEG C are heated to, 137 parts of quality are added dropwise with the speed of 2mL/min
Fraction is 40% formalin, after completion of dropping, is warming up to 95 DEG C, reacts 93min, and cooling obtains final product sticky Bagasse Lignin
Base phenolic resin.
Embodiment 11：
A kind of method of biorefinery Bagasse Lignin base phenolic resin, comprises the following steps：
(1) catalytic degradation of lignin：Count by weight, by 10 parts of Bagasse Lignins, 130 parts of mass fractions are 70% 1,
4 epoxy clustered water solution and 0.6 part of fluorinated graphene assembling silico-tungstic acid nickel are added into microwave reactor, wherein fluorographite
Alkene is 7 with the weight ratio of silico-tungstic acid nickel：1, then stirred with the rotating speed of 300r/min, the power of microwave is controlled for 1000W,
Stop reaction, after natural cooling, the product after being degraded after reacting 33min at 215 DEG C；
(2) purifying of catabolite：By the product after degraded pressure be -0.093MPa, temperature be 50 DEG C under conditions of
Vacuum distillation 4.5h, obtains product after purification；
(3) preparation of phenolic resin：Count by weight, 13 parts of products and 40 parts of phenol after purification are added into reactor
In, stir to form phenols mixed liquor with the rotating speed of 440r/min, 80 DEG C are heated to, 86 parts of quality are added dropwise with the speed of 2mL/min
Fraction is 30% formalin, after completion of dropping, is warming up to 92 DEG C, reacts 96min, and cooling obtains final product sticky Bagasse Lignin
Base phenolic resin.
Embodiment 12：
A kind of method of biorefinery Bagasse Lignin base phenolic resin, comprises the following steps：
(1) catalytic degradation of lignin：Count by weight, by the first that 10 parts of Bagasse Lignins, 300 parts of mass fractions are 90%
Alcohol solution and 1 part of fluorinated graphene assembling Tricesium dodecatungstophosphate are added into microwave reactor, wherein fluorinated graphene and phosphorus tungsten
The weight ratio of sour caesium is 3：1, then stirred with the rotating speed of 300r/min, the power of microwave is controlled for 1000W, at 200 DEG C
Stop reaction, after natural cooling, the product after being degraded after lower reaction 50min；
(2) purifying of catabolite：By the product after degraded pressure be -0.1MPa, temperature be 50 DEG C under conditions of subtract
Pressure distillation 5h, obtains product after purification；
(3) preparation of phenolic resin：Count by weight, 50 parts of products and 50 parts of phenol after purification are added into reactor
In, stir to form phenols mixed liquor with the rotating speed of 500r/min, 80 DEG C are heated to, 137 parts of quality are added dropwise with the speed of 2mL/min
Fraction is 50% formalin, after completion of dropping, is warming up to 95 DEG C, reacts 120min, and cooling obtains final product sticky bagasse wood
Plain base phenolic resin.
Lignin base phenolic resin prepared by the method according to embodiment 1-6, the yield of 4- ethyl -phenols in detection embodiment
And lignin base phenolic resin behavior pattern, all the results are shown in Table 1.
Described above is directed to the detailed description of preferably possible embodiments of the invention, but embodiment is not limited to this hair
Bright patent claim, the equal change completed under the technical spirit suggested by all present invention or modification change, all should belong to
Cover the scope of the claims in the present invention.
Claims (6)
1. a kind of method of biorefinery Bagasse Lignin base phenolic resin, it is characterised in that：Comprise the following steps：
(1) catalytic degradation of lignin：Count by weight, by 10 parts of Bagasse Lignins, 100~300 parts of solvents and 0.01~1 part
Catalyst is added into microwave reactor, is stirred with the rotating speed of 300r/min, the power of microwave is controlled for 1000W, 180
Stop reaction, after natural cooling, the product after being degraded after 20~60min is reacted at~250 DEG C；
(2) purifying of catabolite：By the product after degraded pressure be -0.09~-0.1MPa, temperature be 50 DEG C under conditions of
3~5h of vacuum distillation, obtains product after purification；
(3) preparation of phenolic resin：By in product after purification and phenol addition reactor, stirred with the rotating speed of 400-500r/min
Mix to form phenols mixed liquor, be heated to 80 DEG C, formalin is added dropwise with the speed of 2mL/min, after completion of dropping, be warming up to 90
~95 DEG C, 60~120min is reacted, cooling obtains final product sticky Bagasse Lignin base phenolic resin.
2. the method for a kind of biorefinery Bagasse Lignin base phenolic resin according to claim 1, it is characterised in that：Step
(1) catalyst described in is fluorinated graphene and the assembling thing of heteropolyacid salt；Described fluorinated graphene and the group of heteropolyacid salt
Dress thing be fluorinated graphene assembling Tricesium dodecatungstophosphate, fluorinated graphene assembling silicotungstic acid cesium, fluorinated graphene assembling phosphotungstic acid nickel and
Fluorinated graphene assembling silico-tungstic acid nickel in any one.
3. the method for a kind of biorefinery Bagasse Lignin base phenolic resin according to claim 2, it is characterised in that：It is described
Catalyst in the weight ratio of fluorinated graphene and heteropolyacid salt be 7~9：1~3.
4. the method for a kind of biorefinery Bagasse Lignin base phenolic resin according to claim 1, it is characterised in that：Step
(1) solvent described in is ethanol water, the ring of Isosorbide-5-Nitrae epoxy six that mass fraction is 60~90% that mass fraction is 70~85%
The aqueous solution and mass fraction are any one in 70~90% methanol aqueous solution.
5. the method for a kind of biorefinery Bagasse Lignin base phenolic resin according to claim 1, it is characterised in that：Step
(3) mass fraction of the formalin described in is 15~50% formalin.
6. the method for a kind of biorefinery Bagasse Lignin base phenolic resin according to claim 1, it is characterised in that：Step
(3) the weight ratio of product after purification, phenol and formalin described in is 1~50：19~50：45~137.
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| CN111939899A (en) * | 2020-07-29 | 2020-11-17 | 广东工业大学 | Graphene oxide loaded ruthenium-based catalyst, preparation and application in lignin degradation |
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| CN102838453A (en) * | 2012-08-28 | 2012-12-26 | 华北电力大学 | Method to prepare phenolic organic mixture preparation by means of catalytic pyrolysis of biomass through coke |
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