CN104761695A - Biomass oil modified thermoplastic phenolic resin and preparation method thereof - Google Patents
Biomass oil modified thermoplastic phenolic resin and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of phenolic resin preparation, and in particular relates to biomass oil modified phenolic resin and a preparation method thereof. The method comprises the following steps: fractions at 100-150 DEG C or below and small-molecular products with relatively high reactivity are removed through extraction and distillation, such that biomass oil with a softening point at 60-120 DEG C and suitable for thermoplastic phenolic resin modification is obtained; phenol, biomass oil, aldehyde and an acidic catalyst are sequentially added into a reaction kettle; the pH value of the system is regulated through the addition amount of the acidic catalyst; the temperature is increased to 70-90 DEG C, and is maintained for 1-3h; the temperature is increased to 98-104 DEG C, and boiling reflux is carried out; the temperature is maintained for 1.0-4.0h; when free phenol is qualified, reduced-pressure distillation is carried out, such that the biomass oil modified phenolic resin is obtained. According to the invention, biomass oil components suitable for thermoplastic phenolic resin are adopted, such that the reaction process and product performance are stable. Compared to pure phenolic resin, the prepared resin has the advantages of higher yield, better toughness, lower cost, and better environment friendliness.
Description
Technical field
The present invention relates to resol and prepare field, especially a kind of utilization bio-oil modified thermoplastic resol being applicable to novolac resin and preparation method thereof.
Background technology
Raw material mainly phenol, cresols, xylenol, the Resorcinols etc. of resol, derive from crude oil processing refining, the minimizing day by day of its resource, must make resol increasingly well sold and in short supply.Due to current overexploitation and use, petroleum resources are about to face exhausted danger.
The problem of petroleum resources present situation and environmental development forces us constantly to find and applies new, reproducible equivalent material.At present, the biomass energy that the whole world is researched and developed with all strength is exactly a kind of inexhaustible, nexhaustible renewable energy source.This material, owing to having extensive, the renewable and biodegradable characteristic of raw material, has all taken industrialized paces both at home and abroad.
China's biomass resource amount is huge, about has 700,000,000 tons of agricultural byproducts to can be used as energy utilization.Wherein, agricultural crop straw annual production about 600,000,000 tons; Other agricultural wastes about 1.3 hundred million tons; Forestry biomass resource can be used for power applications about 300,000,000 tons every year; Municipal solid wastes year generation about 2.5 hundred million tons.Compared with fossil energy, biomass energy has environmental friendliness and renewable two large outstanding advantages.
Pyrolysis oil preparation is the main technological approaches of current bioenergy Commercial cultivation, biomass pyrolytic is also known as thermo-cracking or cracking, typically refer under the environment of anaerobic or anoxic, biomass are caused molecular chain to decompose the process producing coke, condensability volatile matter and gaseous product by heat temperature raising, condensability volatile matter is cooled rapidly into flowable liquid, become bio oil or tar, its productive rate is about 40%-60%.Will through further process through pyrogenous origin bio oil crude oil, such as classification, refining and separation, just can obtain gasoline, diesel oil, methyl alcohol, ethanol fuel-oil and Chemicals.The ground such as China Anhui, Shandong and northeast have built up the demo plant of biomass pyrolytic liquefaction, and stable, have ensured the raw material supply of producing bio-oil modified phenolic resins.
The bio oil that current China produces is usually all direct directly to be burnt as low-grade fuel.But, containing materials such as phenols, aldehydes, alcohols, acids in bio-oil, wherein phenols and aldehydes can be used for preparing resol, so both can realize the recycling of relative " waste material " in derived energy chemical field, turn waste into wealth, the complementary production system of recycling economy can be formed again.
But, bio-oil composition is complicated, composition comprises nearly 200 many kinds of substances such as phenols, aldehydes, alcohols, acids, how selectively to utilize bio-oil, become the important topic of current bio-oil research field, the present invention is intended to primordial matter oil by extraction, distillation, remove the cut of less than 100-150 DEG C and the higher small molecules product of reactive behavior, obtaining softening temperature at 60-120 DEG C is applicable to the bio-oil of novolac resin modification, and uses it for the preparation of modified thermoplastic resol.
Summary of the invention
The object of the present invention is to provide the bio-oil modified thermoplastic resol and preparation method thereof of a kind of environmental protection, low cost, stable performance, good combination property, this preparation method is simple, effectively can utilize agricultural wastes, and resin can be widely used in the association areas such as friction materials, precoated sand, grinding materials and grinding tool.
For achieving the above object, the present invention is by the following technical solutions:
The preparation method of bio-oil modified thermoplastic resol, the method take bio-oil as raw material, and employing extraction, distil process prepare the bio-oil being applicable to novolac resin modification, and be applied to the preparation of novolac resin.
Described bio-oil be biomass through pyrogenically prepared oily liquids product, wherein said biomass are selected from any one or a few the mixture comprised in timber, stalk, bamboo wood, bark, maize straw, oak, switchgrass, rice husk.
Through extraction, distil process process bio-oil described in extraction process refer to and utilize solvent mix with bio-oil after, the small molecules in bio-oil is dissolved in solvent, then by removing the insolubles that desolventizing obtains after the separating technology such as precipitating, centrifugal; Described solvent comprises water or organic solvent, preferred deionized water, methylene dichloride or hexanaphthene.
Through extraction, distil process process bio-oil described in distil process refer to as normal pressure or underpressure distillation, and obtain by distillation the cut that boiling point under normal pressure is more than 100 DEG C.Preferred distil process is obtain the cut that boiling point under normal pressure is more than 130 DEG C, further preferably obtains the cut that boiling point under normal pressure is more than 150 DEG C.
The bio-oil modified thermoplastic resol prepared by above method, its molecular weight is 600-1600, and softening temperature is 65-120 DEG C, and degree of mobilization is 25-185mm, and polymerization velocity is 30-130s.
The preparation method of bio-oil modified thermoplastic resol specifically comprises the following steps: by phenol, through the bio-oil of extraction process and distil process process, aldehyde and an acidic catalyst join in reactor successively, wherein the mol ratio of phenol and aldehyde is 1:0.6-8.5, the mass ratio of phenol and bio-oil is 100:20-70, by control an acidic catalyst add-on adjustment system in pH value be 0.5-3.0, according to 5 DEG C/10min heat-up rate to 75-90 DEG C, and be incubated 1-3h, be heated to 98-104 DEG C according to 5 DEG C/10min heat-up rate again and carry out boiling reflux, and be incubated 1.0-4.0h, mensuration system free phenol, reach underpressure distillation after requirement, obtain bio-oil modified thermoplastic resol.Wherein phenol is any one or a few the mixture in phenol, cresols, xylenol, Resorcinol alkylphenol and dihydroxyphenyl propane, aldehyde is any one or a few the mixture in paraformaldehyde, trioxymethylene, formaldehyde, acetaldehyde, furfural, and an acidic catalyst used is any one or a few the mixture in oxalic acid, formic acid, acetic acid, phosphoric acid, tosic acid, p-hydroxybenzenyl sulfonate.
Positively effect of the present invention is embodied in:
(1) production cost of resol, can be reduced with bio-oil Substitute For Partial phenol and aldehyde, in the long term, the problems such as contrast petroleum resources are exhausted and non-renewable, bio-oil adopts sawdust and the agroforestry such as stalk, rice husk by product or waste to be starting material, determines its recyclability and green environmental protection.
(2), present method can will be suitable for the Component seperation of novolac resin modification in primordial matter oil, can the phenol of Some substitute 20-70% and aldehyde, while reduction resol cost, makes resins synthesis reaction process and rosin products stable performance.
(3) the light constituent content in bio-oil intermediate product, can be controlled by separation methods such as extraction, distillations, ensure that bio-oil intermediate product thermochemical property in modified resin production process is stablized, suppress the volatilization of bio-oil light constituent in modified resin production process and in resin solidification, thus improve stability and the eco-environmental prote of resin material.
(4), softening temperature is greater than the yield of the bio-oil modified phenolic resins of 60 DEG C higher than pure phenolic resin yield.
(5), owing to containing long alkyl chain in bio-oil, have self-plasticizing action to resol, comparatively pure phenolic resin is good to make the toughness of bio-oil modified phenolic resins.
(6), use bio-oil to replace part phenol and aldehyde, can reduce the content of free phenol in resol, the cost of wastewater treatment also reduces greatly, and to environment protection, comprehensive utilization of resources, promotes that industry development etc. all has larger pushing effect.
(7), the present invention has that preparation is simple, cost is low, the feature of excellent performance.
Embodiment:
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with embodiment, the present invention is described in further detail, but this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following embodiment.
Embodiment 1:
The extraction of bio-oil and distillation
Bio-oil: viscosity 2700mPa.s is commercially available prod.
1000g bio-oil is joined in there-necked flask, adds distilled water 1000g, start agitator, be warming up to 40 DEG C, insulation 20min, stratification 30min, add distilled water 1000g after removing supernatant liquid, be warming up to 60 DEG C, insulation 40min, stratification 30min, remove supernatant liquid, be heated to 150 DEG C, underpressure distillation, sampling and testing softening temperature reaches 105 DEG C, stops distillation obtaining bio-oil A.
Bio-oil modified thermoplastic resol
Phenol 1000g, bio-oil A 1000g, formaldehyde 707g are joined in reactor successively, start reactor to stir, adjustment temperature in the kettle is 40-50 DEG C, add oxalic acid 15g, according to 5 DEG C/10min heat-up rate to 75 DEG C, and be incubated 1.5h, 98 DEG C of boiling refluxs are heated to again according to 5 DEG C/10min heat-up rate, and be incubated 3.0h, after mensuration system free phenol meets the requirements, start underpressure distillation, vacuum tightness-0.08, after underpressure distillation to resin softening point meets the requirements, obtain bio-oil modified thermoplastic resol.Modified resin yield is 1.15 [yield=total resin weight/(phenol weight+bio-oil weight)], softening temperature is 102 DEG C, and the mass percentage shared by free phenol is 0.74%, and the mass percentage shared by carbon residue is 51.3%, degree of mobilization is 38mm, and polymerization velocity is 31s.
Embodiment 2:
The extraction of bio-oil and distillation
Bio-oil: viscosity is 2100mPa.s is commercially available prod.
1000g bio-oil is joined in there-necked flask, adds distilled water 1000g, start agitator, be warming up to 50 DEG C, insulation 30min, stratification 30min, add distilled water 1000g after removing supernatant liquid, be warming up to 70 DEG C, insulation 20min, stratification 30min, remove supernatant liquid, be heated to 140 DEG C, underpressure distillation, sampling and testing softening temperature reaches 94 DEG C, stops distillation obtaining bio-oil B.
Bio-oil modified thermoplastic resol
Phenol 1000g, bio-oil B 700g, formaldehyde 647g are joined in reactor successively, start reactor to stir, adjustment temperature in the kettle is 40-50 DEG C, add oxalic acid 10g, according to 5 DEG C/10min heat-up rate to 85 DEG C, and be incubated 2h, 102 DEG C of boiling refluxs are heated to again according to 5 DEG C/10min heat-up rate, and be incubated 2h, after mensuration system free phenol meets the requirements, start underpressure distillation, vacuum tightness-0.08, after underpressure distillation to resin softening point meets the requirements, obtain bio-oil modified thermoplastic resol.Modified resin yield 1.12, softening temperature is 93 DEG C, and the mass percentage of free phenol is 1.23%, and the mass percentage shared by carbon residue is 52.4%, and degree of mobilization is 55mm, and polymerization velocity is 47s.
Embodiment 3:
The extraction of bio-oil and distillation
Bio-oil: viscosity 1500mPa.s is commercially available prod.
1000g bio-oil is joined in there-necked flask, adds distilled water 1000g, start agitator, be warming up to 60 DEG C, insulation 15min, stratification 25min, add distilled water 1000g after removing supernatant liquid, be warming up to 70 DEG C, insulation 20min, stratification 30min, remove supernatant liquid, be heated to 130 DEG C, underpressure distillation, sampling and testing softening temperature reaches 82 DEG C, stops distillation obtaining bio-oil C.
Bio-oil modified thermoplastic resol
Phenol 1000g, bio-oil C 500g, formaldehyde 604g are joined in reactor successively, start reactor to stir, adjustment temperature in the kettle is 40-50 DEG C, add oxalic acid 12g, according to 5 DEG C/10min heat-up rate to 85 DEG C, and be incubated 1.5h, 98 DEG C of boiling refluxs are heated to again according to 5 DEG C/10min heat-up rate, and be incubated 4.0h, after mensuration system free phenol meets the requirements, start underpressure distillation, vacuum tightness-0.08, after underpressure distillation to resin softening point meets the requirements, obtain bio-oil modified thermoplastic resol.Modified resin yield is 1.10, and softening temperature is 83 DEG C, and the mass percentage shared by free phenol is 1.56%, and the mass percentage shared by carbon residue is 50.3%, and degree of mobilization is 88mm, and polymerization velocity is 73s.
Embodiment 4:
The extraction of bio-oil and distillation
Bio-oil: viscosity 1100mPa.s is commercially available prod.
1000g bio-oil is joined in there-necked flask, adds distilled water 1000g, start agitator, be warming up to 70 DEG C, insulation 20min, stratification 15min, add distilled water 1000g after removing supernatant liquid, be warming up to 75 DEG C, insulation 20min, stratification 20min, remove supernatant liquid, be heated to 120 DEG C, underpressure distillation, sampling and testing softening temperature reaches 68 DEG C, stops distillation obtaining bio-oil D.
Bio-oil modified thermoplastic resol
Phenol 1000g, bio-oil D 350g, formaldehyde 561g are joined in reactor successively, start reactor to stir, adjustment temperature in the kettle is 40-50 DEG C, add oxalic acid 15g, according to 5 DEG C/10min heat-up rate to 75 DEG C, and be incubated 2.5h, 98 DEG C of boiling refluxs are heated to again according to 5 DEG C/10min heat-up rate, and be incubated 3.5h, after mensuration system free phenol meets the requirements, start underpressure distillation, vacuum tightness-0.08, after underpressure distillation to resin softening point meets the requirements, obtain bio-oil modified thermoplastic resol.Modified resin yield is 1.04, and softening temperature is 71 DEG C, and the mass percentage shared by free phenol is 2.43%, and the mass percentage shared by carbon residue is 51.2%, and degree of mobilization is 182mm, and polymerization velocity is 125s.
As can be seen from embodiment 1-4, along with bio-oil softening temperature reduces (molecular weight reduction), use the yield of the resin of bio-oil modification and softening temperature constantly to reduce, free phenol constantly raises, and polymerization velocity is constantly slack-off.When the softening temperature of bio-oil is reduced to below 60 DEG C, the yield of its modified resin is lower than unmodified yield.
Comparative example 1:
The preparation of resol
Phenol 1000g, formaldehyde 707g are joined successively in reactor, start reactor and stir, adjustment temperature in the kettle is 40-50 DEG C, add oxalic acid 15g, according to 5 DEG C/10min heat-up rate to 75 DEG C, and be incubated 1.5h, then be heated to 98 DEG C of boiling refluxs according to 5 DEG C/10min heat-up rate, and be incubated 3.0h, after mensuration system free phenol meets the requirements, start underpressure distillation, vacuum tightness-0.08, after underpressure distillation to resin softening point meets the requirements, obtain bio-oil modified thermoplastic resol.Modified resin yield is 1.01, and softening temperature is 98 DEG C, free phenol 2.2%, carbon left 52.7%, degree of mobilization 52mm, polymerization velocity 48s.
Comparative example 2:
By phenol 1000g, unprocessed bio-oil 1000g(viscosity 2700mPa.s, for commercially available prod), formaldehyde 707g joins in reactor successively, start reactor to stir, adjustment temperature in the kettle is 40-50 DEG C, add oxalic acid 15g, according to 5 DEG C/10min heat-up rate to 75 DEG C, and be incubated 1.5h, 98 DEG C of boiling refluxs are heated to again according to 5 DEG C/10min heat-up rate, and be incubated 3.0h, after mensuration system free phenol meets the requirements, start underpressure distillation, vacuum tightness-0.08, after underpressure distillation to resin softening point meets the requirements, obtain bio-oil modified thermoplastic resol.Modified resin yield is 0.88, and softening temperature is 92 DEG C, free phenol 2.92%, carbon left 50.8%, degree of mobilization 81mm, polymerization velocity 95s.
Comparative example 3:
The extraction of bio-oil and distillation
Bio-oil: viscosity 2700mPa.s is commercially available prod.
1000g bio-oil is joined in there-necked flask, adds distilled water 1000g, start agitator, be warming up to 40 DEG C, insulation 20min, stratification 30min, add distilled water 1000g after removing supernatant liquid, be warming up to 60 DEG C, insulation 40min, stratification 30min, remove supernatant liquid, be heated to 90 DEG C, underpressure distillation, sampling and testing softening temperature reaches 52 DEG C, stops distillation obtaining bio-oil E.
Bio-oil modified thermoplastic resol
Phenol 1000g, bio-oil E 1000g, formaldehyde 707g are joined in reactor successively, start reactor to stir, adjustment temperature in the kettle is 40-50 DEG C, add oxalic acid 15g, according to 5 DEG C/10min heat-up rate to 75 DEG C, and be incubated 1.5h, 98 DEG C of boiling refluxs are heated to again according to 5 DEG C/10min heat-up rate, and be incubated 3.0h, after mensuration system free phenol meets the requirements, start underpressure distillation, vacuum tightness-0.08, after underpressure distillation to resin softening point meets the requirements, obtain bio-oil modified thermoplastic resol.Modified resin yield is 0.98, and softening temperature is 89 DEG C, and the mass percentage shared by free phenol is 2.64%, and the mass percentage shared by carbon residue is 50.7%, and degree of mobilization is 139mm, and polymerization velocity is 93s.
From embodiment and comparative example: (1) and unmodified resin-phase ratio, the yield that use softening temperature is greater than the rosin products of the bio-oil modification of 60 DEG C is higher, and free phenol is lower; (2) with unmodified resin-phase ratio, use the yield of undressed bio-oil modified resin low many, free phenol is higher, and its reason is that the yield that in bio-oil, active small molecular hinders phenol and formaldehyde reaction to make is lower, and free phenol is higher; (3) with unmodified resin-phase ratio, use softening temperature lower lower than the yield of the bio-oil modified resin of 60 DEG C.
Claims (9)
1. the preparation method of bio-oil modified thermoplastic resol, it is characterized in that: take bio-oil as raw material, employing extraction, distil process prepare the bio-oil being applicable to novolac resin modification, and are applied to the preparation of novolac resin.
2. the preparation method of bio-oil modified thermoplastic resol, it is characterized in that the method comprises the following steps: by phenol, through extraction, the bio-oil of distil process process, aldehyde and an acidic catalyst join in reactor successively, and be 0.5-3.0 by the add-on adjustment system pH controlling an acidic catalyst, 70-90 DEG C is heated to according to the heat-up rate of 5 DEG C/10min, and be incubated 1-3h, be heated to 98-104 DEG C according to 5 DEG C/10min heat-up rate again and carry out boiling reflux, and be incubated 1.0-4.0h, mensuration system free phenol, reach underpressure distillation after requirement, obtain bio-oil modified thermoplastic resol.
3. the preparation method of bio-oil modified thermoplastic resol according to claim 2, is characterized in that: described phenol and the mol ratio of aldehyde are 1:0.6-8.5, phenol with through extracting, the mass ratio of the bio-oil of distil process process is 100:20-70.
4. the preparation method of bio-oil modified thermoplastic resol according to claim 2, it is characterized in that: described phenol is any one or a few the mixture in phenol, cresols, xylenol, Resorcinol alkylphenol and dihydroxyphenyl propane, aldehyde is any one or a few the mixture in paraformaldehyde, trioxymethylene, formaldehyde, acetaldehyde, furfural, and an acidic catalyst used is any one or a few the mixture in oxalic acid, formic acid, acetic acid, phosphoric acid, tosic acid, p-hydroxybenzenyl sulfonate.
5. according to the preparation method of bio-oil modified thermoplastic resol according to claim 1 or claim 2, it is characterized in that: described bio-oil refers to that biomass are through pyrogenically prepared oily liquids product, and wherein said biomass are selected from any one or a few the mixture in timber, stalk, bamboo wood, bark, maize straw, oak, switchgrass, rice husk.
6. according to the preparation method of bio-oil modified thermoplastic resol according to claim 1 or claim 2, it is characterized in that: after described extraction process refers to and utilizes solvent to mix with bio-oil, small molecules in bio-oil is dissolved in solvent, then by removing the technological process that desolventizing obtains insolubles after precipitation and centrifugal separation process.
7. the preparation method of bio-oil modified thermoplastic resol according to claim 6, is characterized in that: the solvent adopted in described extraction process is water or organic solvent.
8. according to the preparation method of bio-oil modified thermoplastic resol according to claim 1 or claim 2, it is characterized in that: described distil process refers to normal pressure or underpressure distillation, wherein obtain by distillation the cut that boiling point under normal pressure is more than 100 DEG C.
9. according to the bio-oil modified thermoplastic resol that the preparation method of bio-oil modified thermoplastic resol according to claim 1 or claim 2 prepares, it is characterized in that: the softening temperature of this bio-oil is 60-120 DEG C, the molecular weight of this resin is 600-1600, softening temperature is 65-120 DEG C, degree of mobilization is 25-185mm, and polymerization velocity is 30-130s.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105860428A (en) * | 2016-05-30 | 2016-08-17 | 四川国能高科生物树脂有限公司 | Biomass oil suitable for modifying thermosetting resin and preparation method thereof |
| CN110586849A (en) * | 2019-09-26 | 2019-12-20 | 宁波新天阳新材料科技有限公司 | Resin precoated sand easy to collapse |
| CN110734529A (en) * | 2019-11-11 | 2020-01-31 | 西南林业大学 | Method for preparing high-ortho thermoplastic phenolic resin from nut shell biomass liquefied substances |
-
2015
- 2015-04-17 CN CN201510182095.8A patent/CN104761695A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105860428A (en) * | 2016-05-30 | 2016-08-17 | 四川国能高科生物树脂有限公司 | Biomass oil suitable for modifying thermosetting resin and preparation method thereof |
| CN105860428B (en) * | 2016-05-30 | 2018-07-27 | 四川国能高科生物树脂有限公司 | A kind of bio-oil and preparation method thereof being modified suitable for thermosetting resin |
| CN110586849A (en) * | 2019-09-26 | 2019-12-20 | 宁波新天阳新材料科技有限公司 | Resin precoated sand easy to collapse |
| CN110734529A (en) * | 2019-11-11 | 2020-01-31 | 西南林业大学 | Method for preparing high-ortho thermoplastic phenolic resin from nut shell biomass liquefied substances |
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