CN101328396A - Eastern larch bark rapid pyrolysis oil modified phenolic resin adhesive - Google Patents
Eastern larch bark rapid pyrolysis oil modified phenolic resin adhesive Download PDFInfo
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- CN101328396A CN101328396A CNA2007101234035A CN200710123403A CN101328396A CN 101328396 A CN101328396 A CN 101328396A CN A2007101234035 A CNA2007101234035 A CN A2007101234035A CN 200710123403 A CN200710123403 A CN 200710123403A CN 101328396 A CN101328396 A CN 101328396A
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Abstract
The invention relates to a preparation method for a low-cost environmentally friendly (low formaldehyde release) larch bark pyrolyzed oil modified phenol-formaldehyde resin adhesive for manufacturing wood composite material. According to the invention, larch bark quickly pyrolyzed oil is used to replace 40 percent of the dosage of phenol, and the pyrolyzed oil modified phenol-formaldehyde resin adhesive is prepared by the means of adding pyrolyzed oil at the middle period to control a mild reaction temperature, and adding formaldehyde and sodium oxide batch by batch. Testing results show that compared with pure phenol-formaldehyde resin, the modified phenol-formaldehyde resin with a pyrolyzed oil substitution rate of 40 percent can reduce the raw material cost by 33 percent and meet the production requirements of plywood and particle boards; the larch bark pyrolyzed oil modified phenol-formaldehyde resin adhesive reaches GB requirements and makes the formaldehyde release reach the environmental protection requirements of E1 grade and even reach the environmental protection standards of E0 if required; and if the particle boards adopt the pyrolyzed oil modified phenol-formaldehyde resin for glue application layer by layer, the thickness of a surface procuring layer can be effectively reduced.
Description
Technical field
The present invention relates to a kind of preparation method who is used to make the pyrolysis oil modified phenolic aldehyde of low-cost environment-friendly (PF) the resin sizing agent of composite wooden material, belong to Materials science and technical field.
Background technology
Sizing agent is the key factor that influences the wood-based plate performance as the important source material of Wood-based Panel Production, and it has significance to performance and its use range of expansion that improves wood-based plate.At present, adhesive for wood accounts for more than 80% of sizing agent of whole timber and wood-based panel industry mainly based on " three aldehyde " glue, and in " three-aldehyde glue ", the PF resin is the second largest adhesive for wood that is only second to the urea-formaldehyde resin consumption.It has excellent Joint strength, excellent water tolerance, thermotolerance and chemical stability, and it is the main glue kind of present outdoor use wood-based plate.Along with Chinese economic development, whole consumption structure forward construction industry tilts, the raising gradually of outdoor use wood-based plate output, and the PF resin has demonstrated wide development space.But from 2000, the phenol price had remarkable rise, and by in April, 2007, domestic phenol price is to reach on the high price about 14000 yuan/t.At the problems referred to above, people have carried out modification widely to the PF resin.Under the prerequisite that guarantees the good physics of PF resin, chemical property, the production cost that reduces the PF resin becomes the focus of research.
China's Woody plant resource is very abundant, and wood residue can reach nearly hundred million t.Yet present wooden resource utilize level still very low, except that being used for fuel and raw material of artifical plate on a small quantity, most of as refuse treatment.With Woody plants such as wood residues is the pyrolysis oil of raw material production, can partly substitute the pyrolysis oil modified PF resin that phenol prepares low-cost environment-friendly, the needs of satisfy not only that China is weather-proof, environment friendly artificial board being produced also are one of most effectual ways of extensive, high-quality, high value added utilization Woody plant resource.Therefore, carrying out bark pyrolysis mechanism and pyrolysis oil modified PF resin preparation process and making sheet Study on Technology thereof in a deep going way has important practical for the development of the artificial board industry of China and is worth.
Chum, it is that raw material has synthesized the PF resin that Helena etc. (1989) adopt biomass pyrolysis oil.They are separated into water-soluble carbohydrate component and the component that is rich in aldehydes matter to rough bio oil by anticipating.The aldehydes matter component washed obtained 20% to 25% phenols and neutral substance after handling with disacidify.Utilize the phenol of these materials alternative 50% to prepare the PF resin.Gel time is between conventional P F resin and resorcinol resin.Yet the pyrolysis oil after this utilization is made with extra care is synthesized the method for PF resin, has increased the cost of this kind PF resin greatly.
The U.S. renewable energy source laboratory (NREL, 1993; Chum H et al, 1993) carried out utilizing timber waste to replace oil to make the research of wood-based plate with sizing agent.This mechanism utilizes sawdust, bark and other biological material, has made " class phenol " oily matter by the cyclone type rapid pyrolysis apparatus, and the aldehydes matter that extracts from this oily matter can replace about 50% phenol to be used for the preparation of PF resin.The pyrolysis oil PF resin of preparation has shown good performance.Equally, the pyrolysis oil after this utilization is refining has increased the cost of this kind PF resin greatly as the method for raw material.
The phenols pyrolysis oil component that X-M.Wang etc. (1997) utilize the pyrolysis of sawdust flash to obtain replaces phenol to prepare glued board PF resin.The formaldehyde that sizing agent adopts and the mol ratio of phenol are respectively 0.9,1.2,1.4, and the mol ratio of NaOH and phenol is 0.3,0.5.Test result and common PF resin contrast.Resin added is 0.15-0.3kg/m
2, sandwich layer gluing, digestion time are 10min.Hot pressing time be 3.5min to 6min, pressure is 1.38MPa, hot pressing temperature is 160 ℃.Shearing resistance and wet wood-breaking rate and the contrast of common PF resin pressing plate.The result shows, F/P is brought up to 1.4 than from 0.9 can improve wet wood-breaking rate, but do not significantly improve dry strength.Improve the water tolerance that the F/P ratio can promote glue.
Kellery, (1997) such as Stephen S adopt the aldehydes matter that is rich in the rapid pyrolysis oil to prepare the PF resin.Different aldehydes matter components has remarkably influenced to the performance of PF resin.Research adopts the aldehydes matter of 25%-45% to replace the phenol monomer to prepare the PF resin, and its performance is similar to general commercial PF resin.Equally, the pyrolysis oil after this utilization is refining has increased the cost of this kind PF resin greatly as the method for raw material.
2000, the technology of pyrolysis oil manufacturing sizing agent was successfully studied by the scientific research group of Greece sizing agent research association.Experimental result shows, the pyrolysis oil after refining can replace 50% phenol to be used to make sizing agent.This novel sizing agent can be used for OSB and plywood production.This group points out that also if will be significantly reduced to this, the replacement amount of phenol will reach 40%, and the price of pyrolysis oil can not be higher than 50% (TSIANRZIS, 2000) of phenol price.
Carlos Amen-Chen, the Felisa Chan (2001) of Canada Laval university and Wang X.M (2001) etc. have carried out the research of coniferous bark vacuum pyrolysis oil PF resin manufacture OSB.They discover that the rich phenols pyrolysis oil that is produced by the bark pyrolysis can replace phenol and formaldehyde reaction to prepare first rank PF resin, are used for the gummed of OSB, and pressing plate experimental results show that its product performance can satisfy Canadian OSB product standard.
The whole softwood bark pyrolysis oil that adopts of Carlos etc. (2002) prepares the PF resin.Different replacement rates, different mol ratio and different alkali numbers are adopted in research.The performance that adopts shaving board to test synthetical glue.Test index comprises, MOR, MOE, dry strength, 2h poach internal bond strength and suction back degree rate of expansion.Homogeneous chipboard adopts the PF resin of 25% and 50% pyrolysis oil substitution rate.Test result is to similar with commercial PF resin pressing plate performance.The PF resin that three layers of shaving board adopts 50% pyrolysis oil substitution rate is as top layer glue, and sandwich layer adopts the PF resin of 25% pyrolysis oil substitution rate, and the shaving board performance has surpassed Canadian standard.
(2002) such as Chan F adopt the pyrolysis oil sizing agent to prepare OSB.The pyrolysis oil that is rich in phenols adopts the vacuum pyrolysis process to produce.It is 25% and 35% that pyrolysis oil substitutes phenol, and preliminary study shows that the dried wet performance of sheet material has satisfied the requirement of CSA 0437 Series 93.Conclusion shows that the phenol of pyrolysis oil alternative 35% is used for the preparation of OSB surface layer adhesive.The PF resin of higher substitution rate its internal bond strength and thickness swelling rate after through 2h, 150 ℃ post-processed have had and have significantly improved.
Domestic research to pyrolysis oil production and application facet at present is also few, and mainly concentrates on the application of pyrolysis oil aspect the energy.To utilizing pyrolysis oil to yet there are no relevant report for the research of feedstock production sizing agent.Along with going deep into of China's sustainable development strategy and pressing for of constructing economical society, the research that utilizes the plant pyrolysis oil to prepare the PF resin has a wide range of applications and development prospect.
Comprehensive present Research is both at home and abroad concluded the direction of pyrolysis oil modified PF resin research: 1. substituted by the refining full oil of pyrolysis oil that turns to gradually of pyrolysis oil; 2. develop to high substitution rate gradually by the low substitution rate of pyrolysis oil.The present invention promptly adopts the full oil of pyrolysis oil to utilize, by improving synthesis technique, in the hope of obtaining the high pyrolysis oil modified PF resin of low-cost environment-friendly of pyrolysis oil substitution rate.
Summary of the invention
The present invention is with the bark of dahurian larch rapid pyrolysis products--and pyrolysis oil is a raw material, utilize its characteristics that contain a large amount of aldehydes matters, part replaces phenol, is used to prepare the pyrolysis oil modified PF resin of low cost, low burst size of methanal, simultaneously, open up new approach for the efficient effectively utilization of pyrolysis oil.
The technical problem that the present invention solves: in order to overcome the excessive problem of pyrolysis oil molecular-weight average,, adopt the feeding mode of pyrolysis oil middle and later periods adding, evenly increase with molecular weight in the whole system in the maintenance sizing agent preparation process in whole glue process; In order to control the reaction severe degree, prevent gel, later stage of preparation has suitably reduced temperature of reaction; For reducing free formaldehyde content, reduced the mol ratio of formaldehyde and phenol, and in whole process of preparation, added formaldehyde in batches; Be the pH value variation of control reaction process, it is synthetic that the method that adopts NaOH in batches to add is carried out resin.
Embodiment
The invention provides a kind of preparation method of pyrolysis oil modified PF resin, specific examples is as follows:
Example one: pyrolysis oil and phenol weight ratio are 40%, formaldehyde: phenol-pyrolysis oil mixture (it is identical with phenol that the mixture molecular weight is thought): the mol ratio of NaOH 1.8: 1: 0.4 adds water and system is contained admittedly reach 50%.The phenol, sodium hydroxide (4/5) and the water that measure are dropped in the reactor simultaneously, stir 10min, temperature rise is to 40-42 ℃ in making, add a part of formaldehyde, in 45min, be warming up to 80-85 ℃, behind the insulation 20min, in 10min, reactant is heated to 90-95 ℃, under this state, keep 15min, be cooled to 75 ℃, add residual formaldehyde, remaining sodium hydroxide and pyrolysis oil, be heated to 78-80 ℃, react, be cooled to 40 ℃ of dischargings to viscosity qualified (400-800cp).
Example two: pyrolysis oil and phenol weight ratio are 40%, formaldehyde: phenol-pyrolysis oil mixture (it is identical with phenol that the mixture molecular weight is thought): the mol ratio of NaOH 1.8: 1: 0.35 adds water and system is contained admittedly reach 50%.The phenol, sodium hydroxide (4/5) and the water that measure are dropped in the reactor simultaneously, stir 10min, temperature rise is to 40-42 ℃ in making, add a part of formaldehyde, in 45min, be warming up to 80-85 ℃, behind the insulation 20min, in 10min, reactant is heated to 90-95 ℃, under this state, keep 15min, be cooled to 75 ℃, add residual formaldehyde, remaining sodium hydroxide and pyrolysis oil, be heated to 80-85 ℃, react, be cooled to 40 ℃ of dischargings to viscosity qualified (400-800cp).
| Index | Conventional P F resin | The PF resin of bark of dahurian larch pyrolysis oil substitution rate 40% |
| Solid content | 50％ | 50％ |
| Viscosity (25 ℃) | 300-600cp | 400-800cp |
| Density (20 ℃) | 1.2g/cm 3 | 1.2g/cm 3 |
| Polymerization time (120 ℃) | 80s | 55s |
| Stability in storage (20 ℃) | ＞60 days | ＞40 days |
| Raw materials cost | 4180 yuan/t | 2840 yuan/t |
Useful effect
Compare with pure PF resin, it is that 40% modification PF resin can reduce cost of material 32% that pyrolysis oil substitutes rate; It is the need of production that 40% modification PF resin can satisfy glued board and particieboard that pyrolysis oil substitutes rate, reaches the GB requirement; Particieboard or the fiberboard burst size of methanal produced with the glutinous agent of this glue satisfy E1The level environmental requirement, and can reach as required E0The level environmental protection standard; If particieboard adopts pyrolysis oil modified PF resin layering applying glue, then can effectively reduce surperficial pre-hardening thickness thickness.
| Performance indications | National standard | Conventional P F resin | The bark of dahurian larch pyrolysis oil substitutes the PF resin of rate 40% |
| Gummed intensity | I class standard (0.7MPa) | 1.12MPa | 0.95MPa |
| Burst size of methanal | E 1Level (＜1.5mg/L) | 1.48mg/L | 0.35-0.9 1mg/L |
Claims (4)
1. preparation method who is applicable to the eastern larch bark rapid pyrolysis oil modified phenolic resin adhesive of the low cost of making composite wooden material, low burst size of methanal, its feature is being: formaldehyde: phenol-pyrolysis oil mixture (it is identical with phenol that the mixture molecular weight is thought): the mol ratio of NaOH is 1.8: 1: 0.35 or 1.8: 1: 0.4.
2. preparation method according to claim 1 is characterized in that: the feeding mode that has proposed " pyrolysis oil adds mid-term " on synthesis technique.
3. preparation method according to claim 2 is characterized in that: in the pyrolysis oil adition process, add residual formaldehyde and remaining sodium hydroxide simultaneously.
4. preparation method according to claim 2 is characterized in that: after feeding intake mid-term, rationally control reaction temperature is between 78-85 ℃.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101602838B (en) * | 2009-07-10 | 2011-01-05 | 北京林业大学 | Method for preparing wood pyrolysis oil modified phenolic resin for artificial board |
| CN105693966A (en) * | 2016-03-21 | 2016-06-22 | 北京林业大学 | Preparation method for pyrolysis oil urea-formaldehyde resin sand solidification agent |
| CN106318294A (en) * | 2016-08-23 | 2017-01-11 | 北京林业大学 | Preparing method of pyrolytic tar resorcinol formaldehyde resin tackifier for use in timberwork building materials |
| CN106674453A (en) * | 2017-01-18 | 2017-05-17 | 吉林三才源生物质能源开发有限公司 | Method for preparing phenolic resin by utilizing maize straw |
| CN108214808A (en) * | 2017-12-29 | 2018-06-29 | 武夷山正华竹木制品有限公司 | A kind of preparation method for being pyrolyzed oil-phenolic resin ecology bamboo powder brick |
| CN110423635A (en) * | 2019-09-12 | 2019-11-08 | 吉林大学 | A kind of method rice husk thermal decomposition power generation and comprehensively utilized |
-
2007
- 2007-06-22 CN CNA2007101234035A patent/CN101328396A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101602838B (en) * | 2009-07-10 | 2011-01-05 | 北京林业大学 | Method for preparing wood pyrolysis oil modified phenolic resin for artificial board |
| CN105693966A (en) * | 2016-03-21 | 2016-06-22 | 北京林业大学 | Preparation method for pyrolysis oil urea-formaldehyde resin sand solidification agent |
| CN105693966B (en) * | 2016-03-21 | 2018-01-12 | 北京林业大学 | A kind of preparation method of pyrolysis oil Lauxite sand-consolidating agent |
| CN106318294A (en) * | 2016-08-23 | 2017-01-11 | 北京林业大学 | Preparing method of pyrolytic tar resorcinol formaldehyde resin tackifier for use in timberwork building materials |
| CN106318294B (en) * | 2016-08-23 | 2019-03-26 | 北京林业大学 | The preparation method of timber structure building materials pyrolysis oil resorcinol formaldehyde resin adhesive |
| CN106674453A (en) * | 2017-01-18 | 2017-05-17 | 吉林三才源生物质能源开发有限公司 | Method for preparing phenolic resin by utilizing maize straw |
| CN108214808A (en) * | 2017-12-29 | 2018-06-29 | 武夷山正华竹木制品有限公司 | A kind of preparation method for being pyrolyzed oil-phenolic resin ecology bamboo powder brick |
| CN108214808B (en) * | 2017-12-29 | 2021-08-10 | 武夷山正华竹木制品有限公司 | Preparation method of pyrolytic oil phenolic resin ecological bamboo powder brick |
| CN110423635A (en) * | 2019-09-12 | 2019-11-08 | 吉林大学 | A kind of method rice husk thermal decomposition power generation and comprehensively utilized |
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