CN110156945A - A kind of preparation method of formaldehydeless biomass-based adhesive - Google Patents
A kind of preparation method of formaldehydeless biomass-based adhesive Download PDFInfo
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- CN110156945A CN110156945A CN201910461482.3A CN201910461482A CN110156945A CN 110156945 A CN110156945 A CN 110156945A CN 201910461482 A CN201910461482 A CN 201910461482A CN 110156945 A CN110156945 A CN 110156945A
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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
- C08G8/28—Chemically modified polycondensates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09J161/14—Modified phenol-aldehyde condensates
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- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention discloses a kind of preparation methods of formaldehydeless biomass-based adhesive, belong to biomass energy chemical field, this method key step is as follows: (1) producing furfuryl aldehyde solution using biomass half cellulose；(2) alkali lignin solution is produced using biomass lignin；(3) biomass phenol is prepared using biomass pyrolytic；(4) the formaldehydeless biomass-based adhesive of function admirable is prepared using biomass phenol, alkali lignin, furfural as raw material again.The problem of present invention solves in existing three-aldehyde glue production technology and prepares adhesive using formaldehyde as raw material, formaldehyde pollution environment provides an effective way to produce Environment-friendlyadhesive adhesive by raw material of biomass.
Description
Technical field
The invention belongs to biomass energy chemical fields, and in particular to a kind of preparation side of formaldehydeless biomass-based adhesive
Method.
Background technique
Currently, adhesion agent for artificial board is mainly formaldehyde series plastics adhesive, i.e. ureaformaldehyde, phenolic aldehyde, melamino-formaldehyde
Glue, but just serious formaldehyde pollution problem is brought because of the extensive use of three formaldehyde resins.The production and use process of three formaldehyde resins
In, it inevitably will appear formaldehyde volatilization problems, not only pollute environment, but also huge harm is caused to human body.Therefore, domestic
Outer scientific research personnel has conducted extensive research in terms of preparing low toxic and environment-friendly resin adhesive, but as long as using formaldehyde as raw material,
Formaldehyde volatilization problems present in adhesive will occur always.
In addition to Formaldehyde, the problem that traditional adhesive also have to be increasingly deficient in face of resource, " three-aldehyde glue " raw material
It is petroleum chemicals, and petroleum is non-renewable resources, the increasingly reserves of reduction necessarily will cause imbalance between supply and demand and intensify, therefore use
Renewable resource replaces non-renewable fossil resource to have become research hotspot.And biomass is because of its reproducibility, low pollution
And abundant generality obtains the approval of people, especially from the point of view of China's status, agriculture proportion is larger, corresponding biomass money
The very abundants such as source such as corncob, corn stover, therefore it is the method killed two birds with one stone that biomass, which is used for adhesive area,.
Occur currently, the research about biomass no-formaldehyde adhesive has some achievements, CN107245315A is disclosed
A kind of preparation method of formaldehydeless biomass-based environmental-protection type adhesive is made by polyvinyl alcohol and 2,5-furandaldehyde condensation
Make protecting colloid condensation polymer, prepares no-formaldehyde adhesive；CN105885773A discloses a kind of wood-based plate biomass without aldehyde glue
Stick and preparation method thereof, biomass, which is placed in modified premixed liquid, stirs and is added the poly- ammonia-epoxychloropropane of polyamide, and acid is adjusted
Filler is added after pH value, target product is made；CN100354386C discloses biomass-based formaldehydeless indoor artificial wood plate
Adhesive and preparation method thereof mixes biomass, oxygen-containing inorganic agent, crosslinking agent and water by high pressure-temperature long agitation
It forms.
Though above method is successfully prepared biomass-based Formaldehyde-free adhesive, still uses a large amount of chemical industry finished products and help
Agent or reaction process are complicated, and reaction condition is more harsh.And it is formaldehydeless biomass-based all to use biomass to produce as raw material
The report of adhesive yet there are no.
Summary of the invention
It is an object of the invention to produce alkali using biomass half cellulose production furfuryl aldehyde solution, using biomass lignin
Lignin liquor is prepared biomass phenol using biomass pyrolytic, then is prepared using biomass phenol, alkali lignin, furfural as raw material
The method of the formaldehydeless biomass-based adhesive of function admirable.
In order to achieve the above objectives, the invention proposes a kind of preparation method of formaldehydeless biomass-based adhesive, features
It is, this method comprises the following steps:
Step 1: preparing furfural aqueous solution:
(1) biomass crushing is placed in reaction kettle, it is molten that the sulfuric acid that concentration is 2wt% is added by solid-to-liquid ratio 1Kg:10L
Liquid is heated to reflux 2h, and filtering obtains hydrolyzate and hydrolysis residue；Adjusting sulfuric acid concentration in hydrolyzate is 2wt%, by solid-to-liquid ratio 1Kg:
Biomass is added in 10L, is heated to reflux 2h, so carries out repeatedly, until obtaining the xylose that xylose concentration is 15wt%~17wt%
Solution；
(2) the catalyst sulfuric acid solution that molar concentration is 2mol/L is added in reactor, adds co-catalyst chlorine
Change sodium to being saturated, stirring forms the rotation liquid level with fixed concentration catalyst and co-catalyst, reflux is warming up to, to anti-
It answers at the uniform velocity to spray in device and adds xylose solution obtained in step (1), xylose generates furfural under the action of catalyst, escapes with steam,
Condensation, obtains furfural aqueous solution；
Step 2: preparation alkali lignin solution:
Hydrolysis residue in step 1 is added with concentration for the NaOH solution of 3wt% the ratio for being 1Kg:10L in solid-to-liquid ratio
Into reaction kettle, heating reflux reaction 2h is down to room temperature, and filtering obtains alkali lignin solution；
Step 3: being modified to alkali lignin:
The alkali lignin solution prepared in step 2 and phenol wastewater are placed in reactor, are warming up to 90 DEG C, constant temperature stirs
Reaction 1.5h is mixed, 60 DEG C is cooled to, prepares alkali lignin modified solution；
Step 4: preparing formaldehydeless biomass-based adhesive:
Furfuryl aldehyde solution and urea are added in the alkali lignin modified solution prepared into step 3, constant temperature stirs 1h, heating
To 98 DEG C and 2h is reacted, is cooled to room temperature vacuum distillation to viscosity >=60mPas, formaldehydeless biomass base rubber is prepared in discharging
Glutinous agent.
Preferably, urea and furfural molar ratio U/F are 2:1,1.5:1,1:1 or 0.5:1 in the step 4.
Preferably, in the step 4 furfural dosage are as follows: m1=M × n × 1.8+N × m2, wherein m1For furfural quality, M
For furfural molal weight, n is the molal quantity of phenol, m2For lignin quality, N=0,0.1,0.3,0.5,0.7 or 0.9.
Further, phenol wastewater is to prepare gained by biomass pyrolytic in the step 3, the specific steps are as follows:
(1) biomass is added in downdraft pyrolysis oven, control pyrolysis temperature is 500 DEG C~700 DEG C, is pyrolyzed as pyrolysis
Gas and pyrolytic carbon；
(2) pyrolysis gas collects the phenol wastewater that pyrolysis generates, phenol wastewater through heat exchanger cooling down to 80 DEG C~90 DEG C
PH value be 8.5, COD COD be 18700mg/L, total organic content be 30wt%~35wt%, the content of phenol
Content for 15.4%, 2- methylphenol is 7.5%.
Preferably, in the step 3 alkali lignin solution and phenol wastewater proportion are as follows: the mass ratio of lignin and phenol
For 7:3,8:2 or 9:1.
Through the above design, the present invention can be brought the following benefits: it is raw that the present invention solves existing three-aldehyde glue
Adhesive is prepared using formaldehyde as raw material in production technology, the problem of formaldehyde pollution environment, to produce environment-friendly type by raw material of biomass
Adhesive provides an effective way.
Further beneficial effect of the invention is:
1, all using biomass as raw material, biomass half cellulose, lignin is made full use of, biomass as resources is improved
The feasibility of comprehensive utilization.
2, chemical industry phenol is replaced with biomass pyrolytic preparation biomass phenol, further gets rid of adhesive preparation and petrochemical industry is produced
The dependence of product.
3, the urea-formaldehyde resin adhesive excellent as raw material processability using biomass phenol, furfural, alkali lignin thoroughly solves
Three-aldehyde glue pollutes the problem of environment, provides an effective way to produce Environment-friendlyadhesive adhesive by raw material of biomass.
Specific embodiment
In order to illustrate more clearly of the present invention, below with reference to preferred embodiment, the present invention is described further.Ability
Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this
The protection scope of invention.In order to avoid obscuring essence of the invention, well known method and process are not described in detail.This hair
Biomass described in bright is rice husk or stalk.
Embodiment 1
Step 1: prepared by furfural aqueous solution
(2) biomass crushing is placed in reaction kettle, it is molten that the sulfuric acid that concentration is 2wt% is added by solid-to-liquid ratio 1Kg:10L
Liquid is heated to reflux 2h, and filtering obtains hydrolyzate and hydrolysis residue；Adjusting sulfuric acid concentration in hydrolyzate is 2wt%, by solid-to-liquid ratio 1Kg:
Biomass is added in 10L, is heated to reflux 2h, such 3 hydrolysis, the xylose solution that production xylose concentration is 16.5wt%；
(2) the sulfuric acid catalysis agent solution that molar concentration is 2mol/L is added in reactor, adds co-catalyst chlorine
Change sodium to being saturated, stirring forms the rotation liquid level with fixed concentration catalyst and co-catalyst, reflux is warming up to, to anti-
It answers at the uniform velocity to spray in device and adds xylose solution obtained in step (1), xylose generates furfural under the action of catalyst, escapes with steam,
Condensation, obtains furfural aqueous solution；
Step 2: prepared by alkali lignin solution
In the ratio of solid-to-liquid ratio 1Kg:10L, the hydrolysis residue in step 1 is added to concentration for the NaOH solution of 3wt%
In reaction kettle, heating reflux reaction 2h is down to room temperature, and filtering obtains alkali lignin solution.
Embodiment 2
Step 1: biomass pyrolytic
Biomass is added in downdraft pyrolysis oven, the air capacity that blower enters pyrolysis oven is adjusted, controls degree of pyrolysis,
Controlling pyrolysis temperature is 500 DEG C~700 DEG C, and pyrolysis obtains pyrolysis gas and pyrolytic carbon；
Step 2: biomass collection phenol
Pyrolysis gas, to 80 DEG C~90 DEG C, collects the phenol wastewater that pyrolysis generates through the indirect cooling down of heat exchanger；It is useless containing phenol
The pH value of water be 8.5, COD COD be 18700mg/L, total organic content be 30wt%~35wt%, main component:
The content of phenol is that the content of 15.4%, 2- methylphenol is 7.5%.
Step 3: alkali lignin solution and embodiment will be prepared in 1 step 2 of embodiment by lignin and phenol mass ratio 7:3
2 step 2 prepare phenol wastewater and are added in reactor, are warming up to 90 DEG C, and constant temperature is stirred to react 1.5h, are cooled to 60 DEG C, preparation
Alkali lignin modified solution out.
Embodiment 3
Furfuryl aldehyde solution and urea are added in the alkali lignin modified solution prepared into embodiment 2, the dosage of furfural is m1
=M × n × 1.8+0.1 × m2, m1For furfural quality, M is furfural molal weight, and n is the molal quantity of phenol, m2For lignin quality,
Urea and furfural molar ratio are 2:1, and constant temperature stirs 1h, is warming up to 98 DEG C and reacts 2h, are cooled to room temperature vacuum distillation to viscosity
>=60mPas, discharging packaging, prepares formaldehydeless biomass-based adhesive.
Embodiment 4
Reacting urea and furfural molar ratio is 1.5:1, and other conditions are consistent with embodiment 3.
Embodiment 5
Reacting urea and furfural molar ratio is 1:1, and other conditions are consistent with embodiment 3.
Embodiment 6
Reacting urea and furfural molar ratio is 0.5:1, and other conditions are consistent with embodiment 3.
Embodiment 7
m1(furfural quality)=M (furfural molal weight) × n (molal quantity of phenol) × 1.8+0.1 × m2(lignin quality),
Without using urea, other conditions are consistent with embodiment 3.
Embodiment 8
m1(furfural quality)=M (furfural molal weight) × n (molal quantity of phenol) × 1.8+0.3 × m2(lignin quality),
Other conditions are consistent with embodiment 7.
Embodiment 9
m1(furfural quality)=M (furfural molal weight) × n (molal quantity of phenol) × 1.8+0.5 × m2(lignin quality),
Other conditions are consistent with embodiment 7.
Embodiment 10
m1(furfural quality)=M (furfural molal weight) × n (molal quantity of phenol) × 1.8+0.7 × m2(lignin quality),
Other conditions are consistent with embodiment 7.
Embodiment 11
Adjusting lignin and phenol mass ratio is 8:2, and other conditions are consistent with embodiment 7.
Embodiment 12
Adjusting lignin and phenol mass ratio is 9:1, and other conditions are consistent with embodiment 7.
Above embodiments and non-present invention full content, therefore other equivalence changes for using the method for the present invention to be carried out,
It should belong to the scope of the patents of the invention.Following table is by embodiment 5 to the 14 formaldehydeless biomass-based adhesive property of gained of embodiment
Index.
| Classification | Bonding strength/MPa | Free aldehyde/% | Free phenol/% |
| Embodiment 3 | 0.75 | It is not detected | 1.38 |
| Embodiment 4 | 0.87 | It is not detected | 1.43 |
| Embodiment 5 | 0.93 | It is not detected | 1.38 |
| Embodiment 6 | 1.14 | It is not detected | 1.49 |
| Embodiment 7 | 1.17 | It is not detected | 1.51 |
| Embodiment 8 | 1.04 | 0.04 | 1.38 |
| Embodiment 9 | 0.95 | 0.07 | 1.22 |
| Embodiment 10 | 0.83 | 0.09 | 1.07 |
| Embodiment 11 | 0.93 | It is not detected | 0.99 |
| Embodiment 12 | 0.82 | 0.03 | 0.53 |
Claims (5)
1. a kind of preparation method of formaldehydeless biomass-based adhesive, which is characterized in that this method comprises the following steps:
Step 1: preparing furfural aqueous solution:
(1) biomass crushing is placed in reaction kettle, the sulfuric acid solution that concentration is 2wt% is added by solid-to-liquid ratio 1Kg:10L, adds
Heat reflux 2h, filtering obtain hydrolyzate and hydrolysis residue；Adjusting sulfuric acid concentration in hydrolyzate is 2wt%, is added by solid-to-liquid ratio 1Kg:10L
Enter biomass, be heated to reflux 2h, so carry out repeatedly, until obtaining the xylose solution that xylose concentration is 15wt%~17wt%；
(2) the catalyst sulfuric acid solution that molar concentration is 2mol/L is added in reactor, adds co-catalyst sodium chloride
To saturation, stirring forms the rotation liquid level with fixed concentration catalyst and co-catalyst, reflux is warming up to, to reactor
Inside xylose solution obtained, xylose generate furfural under the action of catalyst, escape with steam, condense at the uniform velocity in spray plus step (1),
Obtain furfural aqueous solution；
Step 2: preparation alkali lignin solution:
Hydrolysis residue in step 1 is added to instead with concentration for the NaOH solution of 3wt% by the ratio for being 1Kg:10L in solid-to-liquid ratio
It answers in kettle, heating reflux reaction 2h is down to room temperature, and filtering obtains alkali lignin solution；
Step 3: being modified to alkali lignin:
The alkali lignin solution prepared in step 2 and phenol wastewater are placed in reactor, are warming up to 90 DEG C, constant temperature stirring is anti-
1.5h is answered, is cooled to 60 DEG C, prepares alkali lignin modified solution；
Step 4: preparing formaldehydeless biomass-based adhesive:
Furfuryl aldehyde solution and urea are added in the alkali lignin modified solution prepared into step 3, constant temperature stirs 1h, is warming up to 98
DEG C and react 2h, be cooled to room temperature vacuum distillation to viscosity >=60mPas, formaldehydeless biomass-based gluing is prepared in discharging
Agent.
2. the preparation method of the formaldehydeless biomass-based adhesive of one kind according to claim 1, which is characterized in that the step
Urea and furfural molar ratio U/F are 2:1,1.5:1,1:1 or 0.5:1 in rapid four.
3. the preparation method of the formaldehydeless biomass-based adhesive of one kind according to claim 2, which is characterized in that the step
The dosage of furfural in rapid four are as follows: m1=M × n × 1.8+N × m2, wherein m1For furfural quality, M is furfural molal weight, and n is phenol
Molal quantity, m2For lignin quality, N=0,0.1,0.3,0.5,0.7 or 0.9.
4. the preparation method of the formaldehydeless biomass-based adhesive of one kind according to claim 3, which is characterized in that the step
Phenol wastewater is to prepare gained by biomass pyrolytic in rapid three, the specific steps are as follows:
(1) biomass is added in downdraft pyrolysis oven, control pyrolysis temperature is 500 DEG C~700 DEG C, be pyrolyzed as pyrolysis gas and
Pyrolytic carbon；
(2) pyrolysis gas collects the phenol wastewater that pyrolysis generates, the pH of phenol wastewater through heat exchanger cooling down to 80 DEG C~90 DEG C
Value is 8.5, and COD COD is 18700mg/L, and total organic content is 30wt%~35wt%, and the content of phenol is
The content of 15.4%, 2- methylphenol is 7.5%.
5. the preparation method of the formaldehydeless biomass-based adhesive of one kind according to claim 4, which is characterized in that the step
The proportion of alkali lignin solution and phenol wastewater in rapid three are as follows: the mass ratio of lignin and phenol is 7:3,8:2 or 9:1.
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Cited By (3)
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| CN112048259A (en) * | 2020-07-31 | 2020-12-08 | 上海昶法新材料有限公司 | Biomass-based adhesive filler, adhesive, plywood, preparation method and application |
| CN114369435A (en) * | 2022-02-21 | 2022-04-19 | 石河子大学 | Preparation method of biomass-based adhesive and adhesive |
| CN114456754A (en) * | 2022-03-28 | 2022-05-10 | 石河子大学 | Biomass-based phenolic resin adhesive and preparation method thereof |
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| CN112048259A (en) * | 2020-07-31 | 2020-12-08 | 上海昶法新材料有限公司 | Biomass-based adhesive filler, adhesive, plywood, preparation method and application |
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| CN114456754B (en) * | 2022-03-28 | 2023-05-12 | 石河子大学 | Biomass-based phenolic resin adhesive and preparation method thereof |
| CN116285804A (en) * | 2022-03-28 | 2023-06-23 | 石河子大学 | Biomass-based phenolic resin adhesive and preparation method thereof |
| CN116285804B (en) * | 2022-03-28 | 2024-03-29 | 石河子大学 | Biomass-based phenolic resin adhesive and preparation method thereof |
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