CN103924471A - Preparation of modified lignocellulose, and product thereof - Google Patents
Preparation of modified lignocellulose, and product thereof Download PDFInfo
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- CN103924471A CN103924471A CN201410139457.0A CN201410139457A CN103924471A CN 103924471 A CN103924471 A CN 103924471A CN 201410139457 A CN201410139457 A CN 201410139457A CN 103924471 A CN103924471 A CN 103924471A
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Abstract
The invention discloses a preparation method of modified lignocellulose. The preparation method comprises the steps of (1) pre-crushing the lignocellulose raw material; (2) carrying out pretreatment on the pre-crushed lignocellulose raw material; (3) preheating a reaction kettle, feeding the pretreated raw material into the reaction kettle, controlling the pH value in the reaction kettle, filling saturated steam into the reaction kettle, and maintaining the reaction for a period of time at certain temperature under certain pressure; (4) after the reaction, stopping the filling of the steam, and then injecting condensate water into the reaction kettle until the reaction kettle is cooled to the room temperature; and (5) washing, filtering and drying the reactant, and then grinding the product into a certain particle size. The modified lignocellulose prepared by the method has the characteristics of being hydrophobic and high-temperature-resistant, is taken as plastic filler and is especially suitable for engineering plastics.
Description
Technical field
The present invention relates to the wooden cellulosic preparation method of a kind of modification and product thereof.Modification wood fibre prepared by the method has hydrophobic and resistant to elevated temperatures feature, can serve as plastic filler, is specially adapted to engineering plastics.
Background technology
Lignocellulose biomass exists with the form of plant, and main component is cellulose, hemicellulose and lignin.The lignocellulose biomass total amount being generated by photosynthesis every year on the earth exceedes 2,000 hundred million tons, and therefore lignocellulose biomass is renewable resource abundant, the most cheap on the earth.
The easy moisture absorption of thermoplastic composite, the easily expansion prepared as filler using lignocellulose.Can suppress by adding coupling agent although expand, under moist environment, As time goes on material still can expand.In addition,, if do not add in process of production bacteriostatic agent or pesticide, wood plastic composite is easy in soil or under moist environment by microbiologic(al) corrosion.In the process of Wood-plastic material, if heat treatment degree is too fierce, easily there is degraded or produce smell in lignocellulose in addition.While being heated to 160 DEG C as timber, will there is ether bond rupture and generate compound sugar and monose in hemicellulose.Therefore, lignocellulose as filler can be applicable type of polymer less.
Research is found, reduce in a large number or remove in primary lignocellulose except hemicellulose can make material when up to 300 DEG C, extrude or injection molding process in can not produce gas, the simultaneously removal of hemicellulose can make the hydrophily variation (because in material, hydrophobic content of lignin improves) of material.
Summary of the invention
For the problems referred to above, the object of this invention is to provide the wooden cellulosic preparation method of a kind of modification.The modification lignocellulose of preparing by the method has hydrophobic and resistant to elevated temperatures characteristic, can serve as plastic filler, is specially adapted to engineering plastics.
The object of the invention is to be achieved through the following technical solutions:
The wooden cellulosic preparation of a kind of modification, comprises the following steps:
1), by lignocellulosic material precrushing;
2), the lignocellulosic material of precrushing carries out preliminary treatment;
3), by reactor preheating, add pretreated feedstock, control the pH value in reactor, pass into subsequently saturated vapor, react and maintain a period of time under uniform temperature and pressure;
4), after reaction finishes, stop logical steam, pass into subsequently condensed water, until reactor is cooled to normal temperature;
5), reactant through washing, filter, dry, be ground to subsequently certain particle size.
Prepared modification lignocellulose has hydrophobic and resistant to elevated temperatures characteristic, can serve as plastic filler, is specially adapted to engineering plastics.
Preferably, described lignocellulosic material refers to the plant biomass of any type, such as, but not limited to, nonwood plant living beings, imtertilled crop, such as, but not limited to, straw or like vegetable, such as, but not limited to, switchgrass, Value of Spartina Anglica, rye grass, Chinese silvergrass, reed canary grass or its combination; The residue of carbohydrate processing, such as, but not limited to, bagasse, beet pulp or its combination; Agricultural crop straw, such as, but not limited to, paddy, wheat, corn, beans, potato class, oil plant, cotton or its combination; Forestry biomass, such as, but not limited to, firewood forests, the scattered timber in the tending of woods and Chose cutting, residual branch, leaf, wood chip or its combination; Forestry waste material, such as, but not limited to, the branch in logging and process, sawdust, wood shavings, the tip of a branch, slab, butt or its combination; The discarded object of forestry byproducts, such as, but not limited to, shell, fruit stone or its combination.In addition, described lignocellulosic material can comprise Paper or cardboard dead meal, such as but not limited to old and useless newspaper and cardboard etc.Lignocellulosic material can comprise the fiber of a type, also can comprise and come from the former various fibre blends of different lignocelluloses.In addition, described lignocellulosic material can comprise lignocellulosic material, fully dry lignocellulosic material or its combination of fresh lignocellulosic material, local desiccation.In addition, above-mentioned any kind can make novel lignocellulosic material by plant breeding or genetic engineering.
Preferably, the content of cellulose of described lignocellulosic material is approximately greater than 20%, is more preferably approximately greater than 30%, is further preferably and is approximately greater than 40%.In addition, the content of lignin of described lignocellulosic material is approximately greater than 10%, is more typically and is approximately greater than 15%.Described lignocellulosic material also can comprise a small amount of sucrose, fruit sugar and starch.
Preferably, the precrushing method of described lignocellulosic material include but not limited to mill, grind, stir, the mechanically actuated of pulverizing, compression/expansion or other type.Carry out fragmentation by mechanically actuated, can adopt the suitable device of any type, such as but not limited to beater grinder, drum-type crusher, roll press, refiner, mixer grinder, ball mill and vertical grinder.Through above-mentioned break process, the length of at least 80% raw material becomes below 1cm, and preferably the length of at least 90% raw material becomes below 5mm.
Preferably, the preprocess method of described lignocellulosic material is preimpregnation.Described pre-preg reagent is alkali lye, water and dilute acid soln.
Preferably, described alkali lye has NaOH, Na
2cO
3, NaHCO
3, Na
2sO
3or its composition; Described pickle is from sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or its composition.The concentration of described alkali lye or pickle is 0.05～2.5M, preferably 0.1～1.5M.The described preimpregnation time is 10～180min, preferably 30～120min; Described preimpregnation temperature is 40～120 DEG C, preferably 60～100 DEG C; The mass ratio of described presoak and described lignocellulosic material is 1: 5～40, preferably 1: 5～20.
Preferably, the pH value in described reactor is controlled at below 7, preferably 4-6.5; The reaction pressure of described reactor is at 0.5-5MPa, preferably 1-2MPa; Reaction temperature in described reactor is at 150-250 DEG C, preferably 180-220 DEG C; The described reaction time maintains 2～12h, preferably 4-8h.
Preferably, described reactant washs to filtrate and is neutral with deionized water, at 80-120 DEG C, is dried to moisture below 10%.
Preferably, described dried product exhibited is carried out further fragmentation and is sieved.Breaking method includes but not limited to mill, grinds, stirs, the mechanically actuated of pulverizing, compression/expansion or other type.Carry out fragmentation by mechanically actuated, can adopt the suitable device of any type, such as but not limited to beater grinder, drum-type crusher, roll press, refiner, mixer grinder, ball mill and vertical grinder.
Preferably, the precrushing of described lignocellulosic material and dried product exhibited further broken equipment are equipment independently separately, can be identical, and also can difference.
Preferably, described modification lignocellulose, at 30 DEG C, is placed 24h in the climatic chamber that relative humidity is 90%, and its water absorption rate is less than 10%, is preferably less than 5%.
Preferably, the wooden cellulosic decomposition temperature of described modification is greater than 290 DEG C.
Brief description of the drawings
Fig. 1 is thermogravimetric-differential heat determination curve of modification wood fibre.
Fig. 2 is the water absorption rate comparison diagram of modification lignocellulose and untreated lignocellulose.
Detailed description of the invention
Embodiment 1
Get the precomminution of 10kg wood shavings ball mill to crossing 20 mesh sieves; Adding concentration is the hydrochloric acid solution of 0.5M, makes the solid-to-liquid ratio of wood shavings and hydrochloric acid solution reach 1: 10, heating dipping tank to 80 DEG C, and maintain 60min; Reactor is preheated to 150 DEG C, adds macerate, the pH value in control retort, in 5.5 left and right, passes into subsequently saturated vapor to reacting kettle inner pressure and reaches 1.5MPa, and control reactor temperature at 220 DEG C, sustained response 5.5h; After reaction finishes, stop logical steam, pass into subsequently condensed water to reactor and be cooled to normal temperature; Reactant is through washing to filtrate and be neutral with pure water, dried overnight at 80 DEG C, drier 2h is less than 10% to product moisture content at 105 DEG C; Finally extremely cross 100 mesh sieves with grinder grinding product.
The lignocellulose example weight of getting modification for 10mg thermogravimetric-differential heat measure decomposition temperature simultaneously, its condition determination is the mensuration under nitrogen atmosphere, programming rate is 10 DEG C per minute, is alpha-aluminium oxide with reference to sample.Test result as shown in Figure 1, decomposition temperature T
dfor the temperature of the tangent line of weight minimizing beginning temperature of TG curve and the intersection point D of the tangent line of weight minimizing end temp.Calculate decomposition temperature T
dit is 311 DEG C.
Modification lignocellulose and unmodified lignocellulose, at 30 DEG C, are placed to 24h, the calculating water absorption rate of weighing subsequently in the climatic chamber that relative humidity is 90%.As shown in Figure 2, the water absorption rate of the lignocellulose of modification is 4.85% to test result, and unmodified sample water absorption rate is 36.82%.This is due under reaction condition, in lignocellulose easy decomposition composition---first hemicellulose decomposes, and hemicellulose can absorb water.Hemicellulose level reduces, and the lignocellulose water absorption rate of modification declines.
Although embodiment of the present invention are open as above, but it is not restricted to listed utilization in description and embodiment, it can be applied to various applicable the field of the invention completely, for those skilled in the art, can easily realize other amendment, therefore do not deviating under the universal that claim and equivalency range limit, the present invention is not limited to specific details.
Claims (12)
1. the wooden cellulosic preparation of modification, comprises the following steps:
1), by lignocellulosic material precrushing;
2), the lignocellulosic material of precrushing carries out preliminary treatment;
3), by reactor preheating, add pretreated feedstock, control the pH value in reactor, pass into subsequently saturated vapor, react and maintain a period of time under uniform temperature and pressure;
4), after reaction finishes, stop logical steam, pass into subsequently condensed water, until reactor is cooled to normal temperature;
5), reactant through washing, filter, dry, be ground to subsequently certain particle size.
Prepared modification lignocellulose has hydrophobic and resistant to elevated temperatures characteristic, can serve as plastic filler, is specially adapted to engineering plastics.
2. the wooden cellulosic preparation method of a kind of modification according to claim 1 and product thereof, it is characterized in that: described lignocellulosic material refers to the plant biomass of any type, such as, but not limited to, nonwood plant living beings, imtertilled crop, such as, but not limited to, straw or like vegetable, such as, but not limited to, switchgrass, Value of Spartina Anglica, rye grass, Chinese silvergrass, reed canary grass or its combination; The residue of carbohydrate processing, such as, but not limited to, bagasse, beet pulp or its combination; Agricultural crop straw, such as, but not limited to, paddy, wheat, corn, beans, potato class, oil plant, cotton or its combination; Forestry biomass, such as, but not limited to, firewood forests, the scattered timber in the tending of woods and Chose cutting, residual branch, leaf, wood chip or its combination; Forestry waste material, such as, but not limited to, the branch in logging and process, sawdust, wood shavings, the tip of a branch, slab, butt or its combination; The discarded object of forestry byproducts, such as, but not limited to, shell, fruit stone or its combination.In addition, described lignocellulosic material can comprise Paper or cardboard dead meal, such as but not limited to old and useless newspaper and cardboard etc.Lignocellulosic material can comprise the fiber of a type, also can comprise and come from the former various fibre blends of different lignocelluloses.In addition, described lignocellulosic material can comprise lignocellulosic material, fully dry lignocellulosic material or its combination of fresh lignocellulosic material, local desiccation.In addition, above-mentioned any kind can make novel lignocellulosic material by plant breeding or genetic engineering.
3. according to the wooden cellulosic preparation method of a kind of modification described in claim 1,2 and product thereof, it is characterized in that: the content of cellulose of described lignocellulosic material is approximately greater than 20%, be more preferably approximately greater than 30%, be further preferably and be approximately greater than 40%.In addition, the content of lignin of described lignocellulosic material is approximately greater than 10%, is more typically and is approximately greater than 15%.Described lignocellulosic material also can comprise a small amount of sucrose, fruit sugar and starch.
4. the wooden cellulosic preparation method of a kind of modification according to claim 1 and product thereof, is characterized in that: the precrushing method of described lignocellulosic material includes but not limited to mill, grinds, stirs, the mechanically actuated of pulverizing, compression/expansion or other type.Carry out fragmentation by mechanically actuated, can adopt the suitable device of any type, such as but not limited to beater grinder, drum-type crusher, roll press, refiner, mixer grinder, ball mill and vertical grinder.Through above-mentioned break process, the length of at least 80% raw material becomes below 1cm, and preferably the length of at least 90% raw material becomes below 5mm.
5. the wooden cellulosic preparation method of a kind of modification according to claim 1 and product thereof, is characterized in that: the preprocess method of described lignocellulosic material is preimpregnation.Described pre-preg reagent is alkali lye, water and dilute acid soln.
6. according to the wooden cellulosic preparation method of a kind of modification described in claim 1,5 and product thereof, it is characterized in that: described alkali lye has NaOH, Na2CO3, NaHCO3, Na2SO3 or its composition; Described pickle is from sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or its composition.The concentration of described alkali lye or pickle is 0.05～2.5M, preferably 0.1～1.5M.The described preimpregnation time is 10～180min, preferably 30～120min; Described preimpregnation temperature is 40～120 DEG C, preferably 60～100 DEG C; The mass ratio of described presoak and described lignocellulosic material is 1: 5～40, preferably 1: 5～20.
7. the wooden cellulosic preparation method of a kind of modification according to claim 1 and product thereof, is characterized in that: the pH value in described reactor is controlled at below 7, preferably 4-6.5; The reaction pressure of described reactor is at 0.5-5MPa, preferably 1-2MPa; Reaction temperature in described reactor is at 150-250 DEG C, preferably 180-220 DEG C; The described reaction time maintains 2～12h, preferably 4-8h.
8. the wooden cellulosic preparation method of a kind of modification according to claim 1 and product thereof, is characterized in that: described reactant deionized water washs to filtrate and is neutral, at 80-120 DEG C, is dried to moisture below 10%.
9. the wooden cellulosic preparation method of a kind of modification according to claim 1 and product thereof, is characterized in that: described dried product exhibited is carried out further fragmentation and sieved.Breaking method includes but not limited to mill, grinds, stirs, the mechanically actuated of pulverizing, compression/expansion or other type.Carry out fragmentation by mechanically actuated, can adopt the suitable device of any type, such as but not limited to beater grinder, drum-type crusher, roll press, refiner, mixer grinder, ball mill and vertical grinder.
10. according to the wooden cellulosic preparation method of a kind of modification described in claim 1,4,9 and product thereof, it is characterized in that: the precrushing of described lignocellulosic material and dried product exhibited further broken equipment are equipment independently separately, can be identical, also can be different.
The wooden cellulosic preparation method of 11. a kind of modification according to claim 1 and product thereof, it is characterized in that: described modification lignocellulose is at 30 DEG C, relative humidity is 90% the interior 24h of placement of climatic chamber, and its water absorption rate is less than 10%, is preferably less than 5%.
The wooden cellulosic preparation method of 12. a kind of modification according to claim 1 and product thereof, is characterized in that: the wooden cellulosic decomposition temperature of described modification is greater than 290 DEG C.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105457606A (en) * | 2015-12-11 | 2016-04-06 | 上海同化新材料科技有限公司 | Filter aid for metal calendering and rolling oil |
| CN106084852A (en) * | 2016-08-05 | 2016-11-09 | 宁波金特信钢铁科技有限公司 | A kind of preparation method of automobile-used biological engineering plastics |
| CN106117463A (en) * | 2016-06-26 | 2016-11-16 | 吴迪 | A kind of biodegradable oil absorption process for preparing resins |
| CN109728315A (en) * | 2018-12-27 | 2019-05-07 | 华北电力大学 | Modified carbonized celulose cardboard electrode material and microbiological fuel cell |
| CN110628844A (en) * | 2019-09-23 | 2019-12-31 | 福建生物工程职业技术学院 | Graded separation method for cord grass |
| CN110774397A (en) * | 2019-11-22 | 2020-02-11 | 上海同化新材料科技有限公司 | Production system and production method of bleached lignocellulose |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112397850B (en) * | 2020-11-12 | 2022-04-05 | 同济大学 | Modified lignocellulose diaphragm for lithium ion battery and preparation method and application thereof |
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| CN1141373A (en) * | 1995-07-22 | 1997-01-29 | 池洪 | Vegetrable fibre material, and process for preparing same |
| CN1563564A (en) * | 2004-03-16 | 2005-01-12 | 山东轻工业学院 | Method for producing chemical wood pulp |
| CN101068977A (en) * | 2004-10-04 | 2007-11-07 | 梅特索纸业股份有限公司 | Alkaline process and system for producing pulp |
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Patent Citations (3)
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|---|---|---|---|---|
| CN1141373A (en) * | 1995-07-22 | 1997-01-29 | 池洪 | Vegetrable fibre material, and process for preparing same |
| CN1563564A (en) * | 2004-03-16 | 2005-01-12 | 山东轻工业学院 | Method for producing chemical wood pulp |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105457606A (en) * | 2015-12-11 | 2016-04-06 | 上海同化新材料科技有限公司 | Filter aid for metal calendering and rolling oil |
| CN106117463A (en) * | 2016-06-26 | 2016-11-16 | 吴迪 | A kind of biodegradable oil absorption process for preparing resins |
| CN106084852A (en) * | 2016-08-05 | 2016-11-09 | 宁波金特信钢铁科技有限公司 | A kind of preparation method of automobile-used biological engineering plastics |
| CN109728315A (en) * | 2018-12-27 | 2019-05-07 | 华北电力大学 | Modified carbonized celulose cardboard electrode material and microbiological fuel cell |
| CN110628844A (en) * | 2019-09-23 | 2019-12-31 | 福建生物工程职业技术学院 | Graded separation method for cord grass |
| CN110774397A (en) * | 2019-11-22 | 2020-02-11 | 上海同化新材料科技有限公司 | Production system and production method of bleached lignocellulose |
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