CN105951488B - A kind of technique for preparing cellulose using lignocellulosic cleaning - Google Patents

A kind of technique for preparing cellulose using lignocellulosic cleaning Download PDF

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CN105951488B
CN105951488B CN201610516174.2A CN201610516174A CN105951488B CN 105951488 B CN105951488 B CN 105951488B CN 201610516174 A CN201610516174 A CN 201610516174A CN 105951488 B CN105951488 B CN 105951488B
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organic solvent
acid
weak base
cellulose
gas
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CN105951488A (en
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王文雅
王素君
袁其朋
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
    • D21B1/00—Fibrous raw materials or their mechanical treatment
    • D21B1/02—Pretreatment of the raw materials by chemical or physical means
    • D21B1/021—Pretreatment of the raw materials by chemical or physical means by chemical means
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
    • D21B1/00—Fibrous raw materials or their mechanical treatment
    • D21B1/04—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres
    • D21B1/12—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres by wet methods, by the use of steam
    • D21B1/30—Defibrating by other means
    • D21B1/36—Explosive disintegration by sudden pressure reduction
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/20—Pulping cellulose-containing materials with organic solvents or in solvent environment
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

A kind of technique that cellulose is prepared using lignocellulosic cleaning belongs to biological chemical field.This method carries out acid vapor explosion pretreatment using agriculture wood fibre waste as raw material, removes hemicellulose；By gas-explosive material and organic solvent, alkali and water are added in autoclave, and organic solvent concentration is 40~90%, alkali additive amount accounts for the 0.01~0.2% of gas-explosive material, is warming up to 80~280 DEG C, reacts 1~5h at this temperature, cool down after reaction, weak base organic solvent material is obtained by filtration；Peroxy acid is produced by hydrogen peroxide catalyzed carbonic ester and handles weak base organic solvent material, every gram of material adds the hydrogen peroxide of 0.1~0.4mol, and material concentration is 10~100g/L, and 50~90 DEG C of temperature handles 0.5~3h, and filtering washing obtains cellulose.Present invention process combines steam explosion, weak base, organic solvent and hydrogen peroxide catalyzed carbonic ester production peroxy acid, entire process clean environment firendly, economically feasible.

Description

A kind of technique for preparing cellulose using lignocellulosic cleaning
Technical field
The invention belongs to biological chemical fields, are related to a kind of fine using agriculture wood fibre waste cleaning preparation high-purity The method for tieing up element.
Background technology
Cellulose is one of main constituents of biomass material, accounts for 40% or so, is that a kind of nature reserves are most rich Rich reproducible, biodegradable natural polymers.
Cellulose is widely used, and using the cellulose isolated and purified as raw material, can prepare ester derivative and ethers derives Object, available for oil drilling, food, ceramic glaze, daily-use chemical industry, graphite product, coating etc..In addition, it also can be used as Building wood Material, such as dry powder and mortar building materials, inner-outer wall is water-fast Tired powder, binding agent, gap filler etc..The industrial method for preparing cellulose is sub- Sulfate process and alkaline process, both methods are respectively necessary for the aqueous slkali using a large amount of sulphite and high concentration, environmental pollution Serious and later stage water process is difficult.
Invention content
The present invention provides a kind of environmentally protective method for preparing cellulose using agriculture wood fibre waste, including with Lower step：
Prepare the clean method of cellulose, which is characterized in that include the following steps：
(1) it is 1 according to the mass ratio of solid material and liquid using agriculture wood fibre waste as raw material:1~1:6 add Enter the acid solution that mass concentration is 0.1%~1%, placed 1~10 hour at 25~80 DEG C, no absorbed acid is discharged in press filtration Solution obtains the material through low-kappa number；
(2) step (1) material through low-kappa number is delivered to steam blasting machine, by the steam of 0.4~2.0MPa The retention device cylinder of steam blasting machine is passed into, material stops 5~40min in retention device cylinder, and material is pushed to delay Quick-fried device is sprayed in device cylinder tail portion, opens pneumatic ball valve, pressure is made to be down to a standard atmospheric pressure, obtains steam blasting material；
(3) step (2) the steam blasting material is washed, removes the hydrolysate of hemicellulose, drying obtains Remove the gas-explosive material of hemicellulose；
(4) it is 1 according to gas-explosive material and mixed system mass ratio by step (3) gas-explosive material:20~1:5 are added to In mixed system, organic solvent volume percentage is 40~90% in the mixed system, and the mass percentage content of alkali is 0.01 ~0.2%, pyroreaction kettle temperature is risen to 80~280 DEG C, the reaction time is 1~5 hour, is filtered after reaction, 30~ 60 DEG C of drying obtain weak base organic solvent material；
(5) step (4) the weak base organic solvent material is added to carbonic ester according to the material concentration of 5~100g/L In, every gram of weak base organic solvent material adds the hydrogen peroxide of 0.1~0.4mol again, and 0.5 is handled at a temperature of 50~90 DEG C ~3h, filtering washing obtain cellulose.
Preferably, step (1) described raw material sources are corncob, maize straw, bagasse, cotton stalk, grass stalk, cassiri It is one or more in grain.
Preferably, step (1) acid is one or more in sulfuric acid, hydrochloric acid, phosphoric acid, oxalic acid, acetic acid, sulfurous acid.
Preferably, the hydrolysate of the hemicellulose described in step (3) is xylose, arabinose, mannose, galactolipin, Rhamnose.
Preferably, the organic solvent described in step (4) is methanol, in ethyl alcohol, acetone, Isosorbide-5-Nitrae-dioxane, formic acid, acetic acid It is one or more.
Preferably, the alkali described in step (4) is one or more of sodium hydroxide, potassium hydroxide, ammonium hydroxide.
Preferably, reagent of the carbonic ester described in step (5) for all carbonate-containing functional groups, such as dimethyl carbonate, second Base carbonic ester, cyclohexyl carbonic ester etc..
The above technical solution of the present invention has the following advantages over the prior art：
1. the technological parameter that the present invention passes through reasonable design so that entire process route is applicable not only to agriculture wood fibre Waste materials apply also for non-grain crop raw material.
2. the present invention is significantly degraded hemicellulose, is improved cellulose using acid soak and Steam explosion treatment Extraction efficiency.
3. the present invention using organic solvent handle gas-explosive material, clean environment firendly, and using rear organic solvent (methanol, ethyl alcohol, It is one or more in acetone, 1,4- dioxane, formic acid, acetic acid) it can be recycled by rectifying.
4. the present invention produces peroxy acid reaction treatment organic solvent material, product after reaction using hydrogen peroxide catalyzed carbonic ester For methanol, cleaning is feasible, there is wide development space.
Description of the drawings
Fig. 1 cellulose preparation flow figures；
Fig. 2 is the cellulose prepared；
Fig. 3 is the cellulose extracted in the embodiment of the present invention 113C CP/MAS NMR spectras.
Specific embodiment
Following embodiments are merely to illustrate the present invention, but are not limited to the scope of the present invention.
Embodiment 1
Cellulose is prepared by raw material of corncob, specific method is：300g is taken to smash to the corncob of diameter 1cm, is added in 500mL mass fractions are 0.2% dilution heat of sulfuric acid, and 10h is placed at 25 DEG C, and press filtration discharge continues back without the acid solution absorbed With.The corncob of low-kappa number is poured into steam blasting machine, is passed through the steam pressure of 1.0MPa, corncob is in retention device cylinder 10min is stopped, is depressurized to an atmospheric pressure, washing obtains gas-explosive material, dries.The gas-explosive material that 10g is taken to dry, adds ethyl alcohol 90mL adds water 10mL, adds sodium hydroxide 0.2g, 200 DEG C, mixing speed 300rmp is warming up in autoclave, instead Answer 1h.Washing is filtered after being cooled to room temperature, in 40 DEG C of drying.The material after 5g drying is taken to be added in 50mL dimethyl carbonates, 17g hydrogen peroxide is added, 2h is handled at a temperature of 60 DEG C, filtering washing in 40 DEG C of drying, obtains cellulose.Pass through13C CP/MAS nuclear-magnetisms detect spectrogram, and the carbonyl content from hemicellulose is almost nil, shows that hemicellulose level is almost nil, wood Almost inspection does not measure quality, and hemicellulose and lignin are practically free of in the cellulose yet.
Embodiment 2
Cellulose is prepared by raw material of grass stalk, specific method is：300g grass stalks are taken, washing removes dust and impurity, The oxalic acid solution that 1.2L mass fractions are 0.3% is added in, 1h is placed at 80 DEG C, press filtration discharge continues back without the acid solution absorbed With.The grass stalk of low-kappa number is poured into steam blasting machine, is passed through the steam pressure of 0.8MPa, grass stalk is in retention device cylinder 10min is stopped, is depressurized to an atmospheric pressure, washing obtains gas-explosive material, dries.The gas-explosive material that 10g is taken to dry, adds Isosorbide-5-Nitrae-two Six ring 40mL of oxygen, adds water 60mL, adds ammonium hydroxide 0.04g, 180 DEG C are warming up in autoclave, mixing speed is 300rmp reacts 5h.It is filtered after being cooled to room temperature, in 50 DEG C of drying.The material after 5g drying is taken to be added to 80mL carbonic acid diethyls In base ester, hydrogen peroxide 25.5g is added, 0.5h is handled at a temperature of 90 DEG C, filtering washing in 40 DEG C of drying, obtains fiber Element.
Embodiment 3
Cellulose is prepared by raw material of bagasse, specific method is：300g bagasse is taken, washing removes impurity, adds in 1L Mass fraction is 1% phosphoric acid solution, and 6h is placed at 40 DEG C, and press filtration discharge continues reuse without the acid solution absorbed.It will be sour pre- The bagasse of processing pours into steam blasting machine, is passed through the steam pressure of 2.0MPa, and grass stalk stops in retention device cylinder 40min is depressurized to an atmospheric pressure, and washing obtains gas-explosive material, dries.The gas-explosive material that 15g is taken to dry, adds formic acid 30mL, Add water 20mL, add potassium hydroxide 0.01g, 280 DEG C, mixing speed 300rmp are warming up in autoclave, react 3h.It is cold But to filtering after room temperature, in 50 DEG C of drying.The material after 5g drying is taken to be added in 500mL cyclohexyl carbonic esters, adds peroxide Change hydrogen 51g, 3h is handled at a temperature of 50 DEG C, filtering washing in 40 DEG C of drying, obtains cellulose.

Claims (6)

1. a kind of clean method for preparing cellulose, which is characterized in that include the following steps：
（1）It is 1 according to the mass ratio of solid material and liquid using agriculture wood fibre waste as raw material:1~1:6 add in matter A concentration of 0.1%~1% acid solution to be measured, is placed 1~10 hour at 25~80 DEG C, no absorbed acid solution is discharged in press filtration, Obtain the material through low-kappa number；
（2）By step（1）The material through low-kappa number is delivered to steam blasting machine, and the steam of 0.4~2.0MPa is passed through To the retention device cylinder of steam blasting machine, material stops 5~40min in retention device cylinder, and material is pushed to retention device cylinder Quick-fried device is sprayed in body tail portion, opens pneumatic ball valve, pressure is made to be down to a standard atmospheric pressure, obtains steam blasting material；
（3）By step（2）The steam blasting material is washed, and removes the hydrolysate of hemicellulose, and drying is removed The gas-explosive material of hemicellulose；
（4）By step（3）The gas-explosive material is 1 according to gas-explosive material and mixed system mass ratio:20~1:5 are added to mixing In system, organic solvent volume percentage is 40~90% in the mixed system, the mass percentage content of alkali for 0.01~ 0.04%, pyroreaction kettle temperature is risen to 80~280 DEG C, the reaction time is 1~5 hour, is filtered after reaction, 30~60 DEG C drying obtains weak base organic solvent material；
（5）By step（4）The weak base organic solvent material is added to according to the material concentration of 5~100g/L in carbonic ester, often Gram weak base organic solvent material adds the hydrogen peroxide of 0.1~0.4mol again, and 0.5~3h is handled at a temperature of 50~90 DEG C, Filtering washing obtains cellulose, wherein the carbonic ester is dimethyl carbonate, diethyl carbonate or cyclohexyl carbonic ester.
2. clean method according to claim 1, it is characterised in that：Step（1）The raw material sources are corncob, jade It is one or more in rice stalk, bagasse, cotton stalk, grass stalk, cassava grain stillage.
3. clean method according to claim 1, it is characterised in that：Step（1）The acid for sulfuric acid, hydrochloric acid, phosphoric acid, It is one or more in oxalic acid, acetic acid, sulfurous acid.
4. clean method according to claim 1, it is characterised in that：Step（3）The hydrolysate of the hemicellulose It is xylose, arabinose, mannose, galactolipin.
5. clean method according to claim 1, it is characterised in that：Step（4）The organic solvent is methanol, second It is one or more in alcohol, acetone, 1,4- dioxane, formic acid, acetic acid.
6. clean method according to claim 1, it is characterised in that：Step（4）The alkali is sodium hydroxide, hydroxide One or more of potassium, ammonium hydroxide.
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CN106565736B (en) * 2016-11-13 2019-01-04 北京化工大学 A method of Ellagic Acid in Granati Cortex is prepared using steam blasting
CN109423503A (en) * 2017-09-05 2019-03-05 中粮营养健康研究院有限公司 The preprocess method of raw material containing manioc waste
CN109423502A (en) * 2017-09-05 2019-03-05 中粮营养健康研究院有限公司 The recoverying and utilizing method of manioc waste
CN109608553A (en) * 2018-11-12 2019-04-12 中国农业大学 A kind of method that corn stover prepares Triafol T
CN110373927B (en) * 2019-07-15 2021-04-20 徐州工程学院 Method for treating straw biomass raw material based on explosive wave-alkali combination
CN113174770B (en) * 2021-04-27 2022-09-02 中南林业科技大学 Method for pretreating poplar fibers by penetrant synergistic phosphoric acid infiltration coupling steam explosion

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