CN104530385A - Method used for preparing epoxy resin via liquefaction of bagasse pith and phenol - Google Patents
Method used for preparing epoxy resin via liquefaction of bagasse pith and phenol Download PDFInfo
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- CN104530385A CN104530385A CN201410667340.XA CN201410667340A CN104530385A CN 104530385 A CN104530385 A CN 104530385A CN 201410667340 A CN201410667340 A CN 201410667340A CN 104530385 A CN104530385 A CN 104530385A
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Abstract
The invention discloses a method used for preparing epoxy resin via liquefaction of bagasse pith and phenol. The method comprises following steps: (1) bagasse pith powder is weighed and is mixed with phenol, quick lime is added, and an obtained mixture is subjected to preheating for 8 to 12min; (2) concentrated sulfuric acid is added for reaction, an obtained mixed material is cooled, absolute methanol is added, and filtering is carried out; (3) anhydrous magnesium chloride is added, an obtained product is filtered, and is subjected to reduced pressure distillation for 90 to 120min at a temperature of 150 to 180DEG C so as to obtain a bagasse pith phenol liquefied product; (4) 3 to 5g of the bagasse pith phenol liquefied product is collected, and epoxy chloropropane and sodium hydroxide solution are added for reaction; and (5) acetone is added for mixing, filtering is carried out, and an obtained filtrate is subjected to reduced pressure distillation so as to obtain epoxy resin. According to the method, waste bagasse pith obtained via sugar manufacturing is taken as a raw material, and epoxy resin is obtained via phenol liquefaction. The prepared epoxy resin is high in quality, and excellent in curing performance and heat resistance; and in addition, reaction temperature is reduced, and reaction time is shortened, so that energy consumption and production cost are reduced.
Description
Technical field
The present invention relates to a kind of method utilizing biomass Liquefaction Products in Phenol to prepare epoxy resin, particularly a kind of sugarcane marrow Liquefaction Products in Phenol prepares the method for epoxy resin.
Background technology
Bagasse is the by product of sugar enterprise, the main raw material being used as papermaking, but wherein 30% ~ 40% be sugarcane marrow (staple fibre), be mainly used in boiler combustion, utilization ratio is very low.It is Mierocrystalline cellulose that sugarcane marrow mainly forms, and cellulose conversion is the core technology of clean fuel is adopt effective means to be the soluble reducing sugars such as glucose by cellulose hydrolysis.Mierocrystalline cellulose is topmost composition in plant cell wall, is the natural polymer that on the earth, storage is maximum.Mierocrystalline cellulose is the linear homogeneous glycan that D-glucopyranose unit is formed by connecting by the β-glycosidic bond between 1 and 4 of adjacent Tang unit that dewaters, the polymerization degree 8000 ~ 12000.Because cellulosic glucose subunit is easy to form crystallization, directly use chemically reactive lower.The research of natural fiber supramolecular structure is shown, oh groups a large amount of in Mierocrystalline cellulose defines the powerful hydrogen bond of trees, these hydrogen bonds define fine and close crystalline structure, seriously hinder chemical reagent to contact and effect with the effective of cellulose surface, this has become the biggest obstacle of Mierocrystalline cellulose Application and Development.In addition, Mierocrystalline cellulose is wrapped up by xylogen and hemicellulose, and be also that its chemical moiety activity reduces, therefore, Mierocrystalline cellulose is water insoluble, is difficult to hydrolysis, also often needs suitable pre-treatment when chemical treatment.
As far back as the initial stage in last century, front people have just considered how Woody Biomass is prepared liquid fuel and industrial chemicals by liquefaction.Main liquefaction technology is that Woody Biomass, solvent, catalyzer are put into autoclave, passes into hydrogen or carbon monoxide, at high temperature under high pressure by biomass direct liquefaction.Timber, in nineteen twenty-five simulation liquidation of coal process, is used High Pressure Hydrogen reaction solution shape material, is prepared liquid fuel by Fierz under the existence of alkali.During to the oil crisis seventies in last century; the interest of people to plant energy is increased to unprecedented degree; the report of relevant Woody Biomass liquefaction occurs in a large number; what have has also built up the raw petroliferous factory of some experimental plant materials; but because production cost is higher, all fail scale operation.1971, Appell etc. were at 300-350 DEG C, CO or H
2pressure is 14 ~ 24MPa, with Na
2c0
3for catalysis periodical, wood chip is converted into heavy oil.When this method is carried out Wood liquefied, liquefaction oil yield is about 42% of over dry raw material lumber quality.Ultimate analysis shows: carbon containing 76.1% in liquefaction oil, hydrogen 7.3%. oxygen 16.6%, and the relative density of liquefaction oil is 1.10, and the thermo-efficiency represented with the combustion heat ratio of the combustion heat of product and raw material timber is for about 63%.But this liquifying method consumes mass energy, higher to setting requirement, condition is violent, makes reaction comparatively be achieved comparatively difficulty.
Now, crop material carries out liquefying and mostly adopts phenol as liquefied reagent, with or without catalytic liquefaction, and acid catalysis liquefaction process, base catalysis liquefaction process.Simple without catalytic liquefaction method method, but higher to equipment requirements: heat-resisting, withstand voltage, energy consumption is comparatively large, and cost is higher; Acid catalysis liquefaction process has acidity because of catalyzer own, also higher to equipment requirements, needs the cost dropped into also can not estimate; Base catalysis liquefaction process is except to except equipment requirements height, and liquefaction effect is bad, thus it is not good to make to prepare gained epoxy resin quality.
Summary of the invention
The present invention is directed to above-mentioned technical problem, invent a kind of method that sugarcane marrow Liquefaction Products in Phenol prepares epoxy resin, to reach, to prepare gained epoxy resin quality good, and preparation process energy consumption is low, easily realizes, operation, the object such as to reduce costs.
Sugarcane marrow Liquefaction Products in Phenol prepares a method for epoxy resin, comprises following operation steps:
(1) 1:2 ~ 1:6 takes sugarcane marrow powder and phenol mixing respectively in mass ratio, then adds 2 ~ 5g unslaked lime, leaves standstill 10 ~ 20min, 100 ~ 115 DEG C of preheating 8 ~ 12min;
(2) add the vitriol oil to material after preheating in step (1), reaction 10 ~ 90min, then cools gained material rapidly, then adds the anhydrous methanol of 30 ~ 40mL, filters, gets filtrate;
(3) in gained filtrate in step (2), add Magnesium Chloride Anhydrous, filter, get filtrate, keep temperature to be 150 ~ 180 DEG C of underpressure distillation 90 ~ 120min, obtain sugarcane marrow Liquefaction Products in Phenol after product;
(4) take the liquefied substance 3 ~ 5g of sugarcane marrow post liquefaction, add the epoxy chloropropane mixing of 75 ~ 125mL, and then add the sodium hydroxide solution of 15 ~ 25mL, temperature is kept to be 90 ~ 120 DEG C of reaction 3 ~ 5h, add water, leave standstill 20 ~ 30min layering, get supernatant liquid;
(5) in gained clear liquor in step (4), add the acetone of 40 ~ 55mL, mixing, filters, and gained filtrate keeps temperature to be 60 ~ 120 DEG C of underpressure distillation 1 ~ 2h, and after distillation, gained material is epoxy resin.
Wherein, the sugarcane marrow powder described in step (1) is milled after getting sugarcane marrow 60 ~ 80 DEG C of drying 30 ~ 60min, crosses 80 ~ 120 mesh sieves, to obtain final product.
Wherein, the vitriol oil added in step (2) is 0.15g.
Wherein, the mixture of ice and water be cooled to rapidly with less than 0 DEG C described in step (2) cools 10 ~ 20min rapidly.
Wherein, the Magnesium Chloride Anhydrous of 1.2 ~ 1.5g is added in step (3).
Wherein, in step (4), described sodium hydroxide solution mass percent is 30%.
Mierocrystalline cellulose liquefaction mechanism:
Mierocrystalline cellulose component units is sugared ring, and is connected with ehter bond (sugared general key) between sugared ring with sugared ring, and in liquefaction process, first Mierocrystalline cellulose will make the ehter bond between sugared ring element (sugar battalion key) fracture make it be degraded into oligose.The liquefaction process of Mierocrystalline cellulose in phenol, the intermediate product of discovery liquefied product is the light methyl furfural of 5-, oligose and glucose etc., the mechanism proposing Mierocrystalline cellulose liquefaction should be that the ether bond rupture that Mierocrystalline cellulose falls between middle sugared ring generates oligose, be degraded to glucose again, generate the light methyl furfural of 5-further.5-may cause the polymerization of himself and the reaction with phenol through the generation of methyl furfural, until the reaction later stage generates crosslinked macromolecular compound.Its chemical equation is:
Cellulose degradation out in ask that product is easy to phenol generation condensation reaction in acid condition, following formula is Mierocrystalline cellulose liquefied product and the contingent reaction of phenol
It is the polymer of epoxy compounds.Except the ether bond rupture between sugared ring and sugared ring is more sugared ring ring-opening reaction in various degree in liquefaction process.Epoxy compounds is open loop under nucleophilic reagent attack easily, removes an external force.
Compared with prior art, beneficial effect of the present invention:
The waste sugarcane marrow that the present invention utilizes sugaring to produce is as raw material, and after Liquefaction Products in Phenol, preparation generates epoxy resin, and it is good that the present invention prepares gained epoxy resin quality, has better solidified nature, thermotolerance etc.; Further, add unslaked lime in the methods of the invention, help lend some impetus to sugarcane marrow Liquefaction Products in Phenol, reduce temperature of reaction, shorten the reaction times, thus reduce energy consumption and production cost.
Embodiment
Further describe the present invention referring to embodiment, to make those skilled in the art can implement according to this with reference to specification sheets word, scope is not limited by embodiments of the present invention.
Embodiment 1
Mill after getting sugarcane marrow 60 DEG C of dry 60min, cross 80 mesh sieves after milling, gained is sugarcane marrow powder, for subsequent use.1:2 takes sugarcane marrow powder 4g respectively in mass ratio, phenol 8g mixes, add the mixing of 2g unslaked lime again, leave standstill 10min, 100 DEG C of preheating 12min, then the vitriol oil of 0.15g is added, reaction 10min, then cools 10min rapidly with the mixture of ice and water of less than 0 DEG C, then adds the anhydrous methanol of 30mL, filter with enamel funnel, get filtrate; In filtrate, add 1.2g Magnesium Chloride Anhydrous, filter with enamel funnel, get filtrate and put into there-necked flask and keep temperature to be 150 DEG C of underpressure distillation 120min, obtain sugarcane marrow Liquefaction Products in Phenol after product.
Take the liquefied substance 3g of sugarcane marrow post liquefaction, add the epoxy chloropropane mixing of 75mL, and then the massfraction adding 15mL is the sodium hydroxide solution of 30%, keep temperature to be 90 DEG C of reaction 5h, add water, leave standstill 30min layering, get supernatant liquid; In clear liquor, add the acetone of 40mL, mixing, filter, get filtrate, keep temperature to be 60 DEG C of underpressure distillation 2h, after distillation, gained material is epoxy resin.
Embodiment 2
Mill after getting sugarcane marrow 70 DEG C of dry 45min, cross 100 mesh sieves after milling, gained is sugarcane marrow powder, for subsequent use.1:4 takes sugarcane marrow powder 4g respectively in mass ratio, phenol 16g mixes, add the mixing of 3.5g unslaked lime again, leave standstill 15min, 110 DEG C of preheating 10min, then the vitriol oil of 0.15g is added, reaction 50min, then cools 15min rapidly with the mixture of ice and water of less than 0 DEG C, then adds the anhydrous methanol of 35mL, filter with enamel funnel, get filtrate; In filtrate, add 1.5g Magnesium Chloride Anhydrous, filter with enamel funnel, get filtrate and put into there-necked flask and keep temperature to be 165 DEG C of underpressure distillation 115min, obtain sugarcane marrow Liquefaction Products in Phenol after product.
Take the liquefied substance 4g of sugarcane marrow post liquefaction, add the epoxy chloropropane mixing of 90mL, and then the massfraction adding 20mL is the sodium hydroxide solution of 30%, keep temperature to be 115 DEG C of reaction 4h, add water, leave standstill 20min layering, get supernatant liquid; In clear liquor, add the acetone of 45mL, mixing, filter, get filtrate, keep temperature to be 90 DEG C of underpressure distillation 1.5h, after distillation, gained material is epoxy resin.
Embodiment 3
Mill after getting sugarcane marrow 80 DEG C of dry 30min, cross 120 mesh sieves after milling, gained is sugarcane marrow powder, for subsequent use.1:6 takes sugarcane marrow powder 4g respectively in mass ratio, phenol 24g mixes, add the mixing of 5g unslaked lime again, leave standstill 20min, 115 DEG C of preheating 8min, then the vitriol oil of 0.15g is added, reaction 90min, then cools 20min rapidly with the mixture of ice and water of less than 0 DEG C, then adds the anhydrous methanol of 40mL, filter with enamel funnel, get filtrate; In filtrate, add 1.5g Magnesium Chloride Anhydrous, filter with enamel funnel, get filtrate and put into there-necked flask and keep temperature to be 180 DEG C of underpressure distillation 90min, obtain sugarcane marrow Liquefaction Products in Phenol after product.
Take the liquefied substance 5g of sugarcane marrow post liquefaction, add the epoxy chloropropane mixing of 125mL, and then the massfraction adding 25mL is the sodium hydroxide solution of 30%, keep temperature to be 120 DEG C of reaction 3h, add water, leave standstill 25min layering, get supernatant liquid; In clear liquor, add the acetone of 55mL, mixing, filter, get filtrate, keep temperature to be 120 DEG C of underpressure distillation 1h, after distillation, gained material is epoxy resin.
The waste sugarcane marrow that the present invention utilizes sugaring to produce is as raw material, and after Liquefaction Products in Phenol, preparation generates epoxy resin, and it is good that the present invention prepares gained epoxy resin quality, has better solidified nature, thermotolerance etc.; Further, add unslaked lime in the methods of the invention, help lend some impetus to sugarcane marrow Liquefaction Products in Phenol, reduce temperature of reaction, shorten the reaction times, thus reduce energy consumption and production cost.
Claims (6)
1. sugarcane marrow Liquefaction Products in Phenol prepares a method for epoxy resin, it is characterized in that, comprises following operation steps:
(1) 1:2 ~ 1:6 takes sugarcane marrow powder and phenol mixing respectively in mass ratio, then adds 2 ~ 5g unslaked lime, 100 ~ 115 DEG C of preheating 8 ~ 12min;
(2) add the vitriol oil to material after preheating in step (1), reaction 10 ~ 90min, then cools gained material rapidly, then adds the anhydrous methanol of 30 ~ 40mL, filters, gets filtrate;
(3) in gained filtrate in step (2), add Magnesium Chloride Anhydrous, filter, get filtrate, keep temperature to be 150 ~ 180 DEG C of underpressure distillation 90 ~ 120min, obtain sugarcane marrow Liquefaction Products in Phenol after product;
(4) take the liquefied substance 3 ~ 5g of sugarcane marrow post liquefaction, add the epoxy chloropropane mixing of 75 ~ 125mL, and then add the sodium hydroxide solution of 15 ~ 25mL, temperature is kept to be 90 ~ 120 DEG C of reaction 3 ~ 5h, add water, leave standstill 20 ~ 30min layering, get supernatant liquid;
(5) in gained clear liquor in step (4), add the acetone of 40 ~ 55mL, mixing, filters, and gained filtrate keeps temperature to be 60 ~ 120 DEG C of underpressure distillation 1 ~ 2h, and after distillation, gained material is epoxy resin.
2. sugarcane marrow Liquefaction Products in Phenol prepares the method for epoxy resin according to claim 1, it is characterized in that: the sugarcane marrow powder described in step (1) is milled after getting sugarcane marrow 60 ~ 80 DEG C of drying 30 ~ 60min, crosses 80 ~ 120 mesh sieves, to obtain final product.
3. sugarcane marrow Liquefaction Products in Phenol prepares the method for epoxy resin according to claim 1, it is characterized in that: the vitriol oil added in step (2) is 0.15g.
4. sugarcane marrow Liquefaction Products in Phenol prepares the method for epoxy resin according to claim 1, it is characterized in that: the mixture of ice and water be cooled to rapidly with less than 0 DEG C described in step (2) cools 10 ~ 20min rapidly.
5. sugarcane marrow Liquefaction Products in Phenol prepares the method for epoxy resin according to claim 1, it is characterized in that: the Magnesium Chloride Anhydrous adding 1.2 ~ 1.5g in step (3).
6. sugarcane marrow Liquefaction Products in Phenol prepares the method for epoxy resin according to claim 1, it is characterized in that: in step (4), and described sodium hydroxide solution mass percent is 30%.
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| CN201410667340.XA CN104530385A (en) | 2014-11-20 | 2014-11-20 | Method used for preparing epoxy resin via liquefaction of bagasse pith and phenol |
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| CN201410667340.XA CN104530385A (en) | 2014-11-20 | 2014-11-20 | Method used for preparing epoxy resin via liquefaction of bagasse pith and phenol |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1109280A (en) * | 1993-12-27 | 1995-10-04 | 株式会社林原生物化学研究所 | Alkali-treated bagasse, and its prepartion and uses |
| CN101619227A (en) * | 2008-06-30 | 2010-01-06 | 淮北中润生物能源技术开发有限公司 | Direct liquifying method of cellulose biomass |
| US20110272108A1 (en) * | 2010-05-07 | 2011-11-10 | Basf Se | Process for producing pulp and at least one organic liquid or liquefiable material of value with offgas recycling |
| CN103992497A (en) * | 2014-04-22 | 2014-08-20 | 南京林业大学 | Method for preparing biomass-based foam materials from natural fiber biomass materials |
-
2014
- 2014-11-20 CN CN201410667340.XA patent/CN104530385A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1109280A (en) * | 1993-12-27 | 1995-10-04 | 株式会社林原生物化学研究所 | Alkali-treated bagasse, and its prepartion and uses |
| CN101619227A (en) * | 2008-06-30 | 2010-01-06 | 淮北中润生物能源技术开发有限公司 | Direct liquifying method of cellulose biomass |
| US20110272108A1 (en) * | 2010-05-07 | 2011-11-10 | Basf Se | Process for producing pulp and at least one organic liquid or liquefiable material of value with offgas recycling |
| CN103992497A (en) * | 2014-04-22 | 2014-08-20 | 南京林业大学 | Method for preparing biomass-based foam materials from natural fiber biomass materials |
Non-Patent Citations (1)
| Title |
|---|
| 张文明等: "麦秆液化物环氧树脂的制备与表征", 《信息记录材料》 * |
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Application publication date: 20150422 |