CN110373441B - Preparation method of high-length-diameter ratio nanocellulose - Google Patents
Preparation method of high-length-diameter ratio nanocellulose Download PDFInfo
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- CN110373441B CN110373441B CN201910495037.9A CN201910495037A CN110373441B CN 110373441 B CN110373441 B CN 110373441B CN 201910495037 A CN201910495037 A CN 201910495037A CN 110373441 B CN110373441 B CN 110373441B
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/04—Polysaccharides, i.e. compounds containing more than five saccharide radicals attached to each other by glycosidic bonds
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/14—Preparation of compounds containing saccharide radicals produced by the action of a carbohydrase (EC 3.2.x), e.g. by alpha-amylase, e.g. by cellulase, hemicellulase
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- 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
- D21C5/005—Treatment of cellulose-containing material with microorganisms or enzymes
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21D—TREATMENT OF THE MATERIALS BEFORE PASSING TO THE PAPER-MAKING MACHINE
- D21D1/00—Methods of beating or refining; Beaters of the Hollander type
- D21D1/02—Methods of beating; Beaters of the Hollander type
Abstract
The invention provides a preparation method of high-length-diameter ratio nanocellulose, which comprises the steps of treating lignocellulose by composite biological enzyme, pulping the treated lignocellulose to a certain pulping degree by a pulping machine, adding a proper amount of dispersing agent or ground mineral substances into the obtained pulp, performing colloid mill circulation treatment, and continuously reducing the gap of a grinding disc along with the increase of the circulation times to obtain the high-length-diameter ratio nanocellulose. The invention overcomes the problems of high energy consumption required for preparing the nano-cellulose and agglomeration of the nano-cellulose with high length-diameter ratio caused by hydrogen bond action in the preparation process.
Description
Technical Field
The invention relates to a preparation method of nanocellulose with a high length-diameter ratio, belonging to the field of biological nano materials.
Background
With the continuous development of social economy, the problems of non-renewable resources are increasingly deficient, environmental pollution and the like are increasingly prominent, and wood fibers as abundant renewable resources on the earth are increasingly emphasized in the fields of science, medicine, energy, health and the like. The nano-cellulose is a cellulose derivative material with one-dimensional nano-size prepared by a chemical, physical or biological method by using a fiber material as a raw material, and can be used in the fields of medicines, packaging, papermaking, food additives, paint coatings, floors, building materials and the like due to the excellent characteristics of biodegradability, biocompatibility, large specific surface area, excellent mechanical properties and the like.
As an emerging biological nanomaterial, nanocellulose has received a wide range of attention. The preparation method thereof is divided into a chemical method, a physical method, a biological method and the like. The chemical method for preparing the nano-cellulose comprises an inorganic acid hydrolysis method and a cellulose hydrolysis method. The inorganic acid hydrolysis method utilizes strong acid to realize the hydrolysis of cellulose, improves the product yield by adopting modes such as ultrasonic pretreatment and the like, and shortens the reaction time; the temperature, reaction time, type and concentration of strong acid, dosage of plant cellulose and the like in the hydrolysis process all influence the properties of the nano-cellulose, a large amount of waste acid and impurities are generated by the method, a large amount of water and power resources are consumed, the requirement on reaction equipment is high, the equipment is required to be capable of tolerating the strong acid, and in addition, the residues after the reaction are difficult to recover and treat. The cellulose enzyme hydrolysis method, namely, cellulose with strong selectivity is used for removing the amorphous area of cellulose and leaving the crystalline area of cellulose, and the method has mild process conditions and strong specificity. The physical method is to separate and decompose cellulose by physical means such as pressure, friction, heating explosion and the like to prepare the nano-scale cellulose. The method has simple process and easy operation, but needs special equipment, has higher energy consumption, wide particle size distribution of the prepared nano-cellulose, is easy to cause the problems of blockage of a homogenizer and the like, and can not realize the continuity of the preparation process. The biological method for preparing the nano-cellulose has the advantages of complex operation, long time consumption and high cost, and is not widely applied in spite of more researches at home and abroad. Therefore, researches and developments of a novel simple, green, low-energy-consumption and high-efficiency method for preparing nano-cellulose are not easy.
Disclosure of Invention
The invention aims to provide a preparation method of nanocellulose with high length-diameter ratio, which has low energy consumption and can effectively solve the problem of nanocellulose agglomeration.
The technical scheme adopted by the invention is as follows: a preparation method of high-length-diameter-ratio nano cellulose is characterized in that wood fibers with a certain concentration are treated by composite biological enzyme for 12-48 hours under the conditions that the temperature is 25-50 ℃ and the pH value is 6.5-8.5, treated pulp is diluted to the concentration of 1.5-2.5 w% by adding water and then is pulped by a beater until the pulping degree is 65-95 DEG SR, 0.1-1 w ‰ of dispersing agent or grinded mineral matter with the particle diameter of 10-200nm is added into the obtained pulp according to the absolute dry weight of the wood fibers, and then colloid mill circulation treatment is carried out, the circulation frequency is 2-10 times, and the gaps between millstones are continuously reduced along with the increase of the circulation frequency, so that the high-length-diameter-ratio nano cellulose with the length-diameter ratio of 500-2000 is obtained.
The preparation method of the high-length-diameter ratio nanocellulose is characterized in that the lignocellulose is one or more of softwood pulp, hardwood pulp or bamboo pulp.
The preparation method of the high-length-diameter ratio nanocellulose is characterized in that the concentration of lignocellulose is 2-5%.
The preparation method of the high-length-diameter ratio nanocellulose is characterized in that the compound biological enzyme is prepared by compounding endoglucanase, exoglucanase and beta-glucosidase according to the proportion of 10-30: 5-20: 1-5.
The preparation method of the high-length-diameter ratio nanocellulose is characterized in that the addition amount of the composite biological enzyme is 50-150 ppm relative to the absolute dry weight of wood fiber.
The preparation method of the nanocellulose with the high length-diameter ratio is characterized in that the dispersing agent is polyethylene oxide (PEO) or Polyacrylamide (PAM).
The preparation method of the high-length-diameter ratio nanocellulose is characterized in that the mineral substance is one or a mixture of more of talcum powder, kaolin or titanium dioxide.
By adopting the method, the energy consumption can be effectively reduced through the complex enzyme treatment, the agglomeration problem of the nano-cellulose is solved in the pulping and grinding processes, and the preparation method is green and environment-friendly.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
First, an embodiment is described.
The preparation method of the high-length-diameter ratio nanocellulose comprises the following steps: weighing 1000g of softwood pulp, adding water until the pulp concentration is 2%, treating for 12h under the condition that the pH value is 6.5 and the temperature is 25 ℃, adding 150ppm of composite biological enzyme (formed by compounding endoglucanase, exoglucanase and beta-glucosidase according to the proportion of 10: 5: 1), diluting the treated pulp to the concentration of 1.5w%, pulping to the pulping degree of 65 DEG SR by using a tile-power pulping machine, adding 0.1w ‰ of polyoxyethylene into the obtained pulp, uniformly stirring, performing circulation treatment in a colloid mill, reducing the millstone gap once every two times of circulation, and performing circulation grinding for 2 times to obtain the nano-cellulose with the length-diameter ratio of 500-1000.
Second, embodiment two.
The preparation method of the high-length-diameter ratio nanocellulose comprises the following steps: weighing 1000g of softwood pulp, adding water until the pulp concentration is 3%, treating for 24h under the condition of 30 ℃ and pH 7.5 by 100ppm of composite bio-enzyme (prepared by compounding endoglucanase, exoglucanase and beta-glucosidase according to the proportion of 15: 10: 5), diluting the treated pulp to the concentration of 2w%, pulping by using a tile power pulping machine until the pulping degree is 75 DEG SR, adding 0.5w ‰ of polyacrylamide into the obtained pulp, uniformly stirring, performing circulation treatment in a colloid mill, reducing the millstone gap twice per circulation, and performing circulation grinding for 4 times to obtain the nano-cellulose with the length-diameter ratio of 800-1200.
And III, embodiment III.
The preparation method of the high-length-diameter ratio nanocellulose comprises the following steps: weighing 500g of softwood pulp and 500g of hardwood pulp, adding water until the pulp concentration is 4%, treating the mixture for 48 hours at 40 ℃ and pH of 6.5 by 50ppm of composite bio-enzyme (formed by compounding endoglucanase, exoglucanase and beta-glucosidase according to the ratio of 30: 20: 5), adding water into the treated pulp to dilute the treated pulp to the concentration of 2.5w%, pulping the pulp by using a watt-force pulping machine until the pulping degree is 85 DEG SR, adding 0.5w thousandth of polyoxyethylene into the obtained pulp, uniformly stirring, performing circulation treatment in a colloid mill, reducing the millstone gap once every two times of circulation, and performing circulation grinding for 6 times to obtain the nano-cellulose with the length-diameter ratio of 800-1500.
Fourth, the fourth embodiment.
The preparation method of the high-length-diameter ratio nanocellulose comprises the following steps: weighing 500g of softwood pulp and 500g of hardwood pulp, adding water until the pulp concentration is 5%, treating for 48h under the condition of 50 ℃ and pH of 8.5 by 100ppm of composite bio-enzyme (formed by compounding endoglucanase, exoglucanase and beta-glucosidase according to the proportion of 15: 10: 3), diluting the treated pulp to the concentration of 1.5w%, pulping by using a tile power beater until the pulping degree is 95 DEG SR, adding 0.1w ‰ of ground talcum powder with the particle diameter of 10-200nm into the obtained pulp, uniformly stirring, performing circulation treatment in a colloid mill, reducing the millstone gap once every two times of circulation, and performing circulation grinding for 8 times to obtain the nanocellulose with the length-diameter ratio of 1000-2000.
And fifthly, the fifth embodiment.
The preparation method of the high-length-diameter ratio nanocellulose comprises the following steps: weighing 500g of softwood pulp and 500g of hardwood pulp, adding water until the pulp concentration is 5%, treating for 48h under the condition of 50 ℃ and pH of 8.5 by 150ppm of composite bio-enzyme (formed by compounding endoglucanase, exoglucanase and beta-glucosidase according to the proportion of 10: 15: 1), diluting the treated pulp by adding water to the concentration of 2w%, pulping by using a tile-power pulping machine until the pulping degree is 95 DEG SR, adding 0.5w ‰ of ground kaolin with the particle diameter of 10-200nm into the obtained pulp, uniformly stirring, performing circulation treatment in a colloid mill, reducing the millstone gap once every two times, and performing circulation grinding for 10 times to obtain the nano-cellulose with the length-diameter ratio of 1200-2000.
Sixthly, embodiment six.
The preparation method of the high-length-diameter ratio nanocellulose comprises the following steps: weighing 1000g of hardwood pulp, adding water until the pulp concentration is 5%, treating for 48h under the condition of 50 ℃ and pH 8.5 by 100ppm of composite biological enzyme (prepared by compounding endoglucanase, exoglucanase and beta-glucosidase according to the proportion of 15: 2), diluting the treated pulp to the concentration of 2.5w%, pulping by using a tile-power pulping machine until the pulping degree is 95 DEG SR, adding 1w ‰ of ground talcum powder and titanium dioxide powder mixture with the particle diameter of 10-200nm into the obtained pulp, uniformly stirring, performing circulation treatment in a colloid mill, reducing the grinding disc gap twice per circulation, and performing circulation grinding for 10 times to obtain the nano-cellulose with the length-diameter ratio of 1200-2000.
Seventhly, embodiment seven.
The preparation method of the high-length-diameter ratio nanocellulose comprises the following steps: weighing 1000g of bamboo pulp, adding water until the pulp concentration is 5%, treating for 48h by 150ppm of composite biological enzyme (prepared by compounding endoglucanase, exoglucanase and beta-glucosidase at a ratio of 25: 15: 5) under the condition of 50 ℃ and pH 7.0, adding water to dilute the treated pulp to a concentration of 2.5w%, pulping by using a tile-power pulping machine until the pulping degree is 95 DEG SR, adding 1w ‰ of ground talcum powder, kaolin and titanium dioxide mixture with the particle diameter of 10-200nm into the obtained pulp, stirring uniformly, performing circulation treatment in a colloid mill, reducing the gap of a grinding disc for two times per circulation, and performing circulation grinding for 10 times to obtain the nano-cellulose with the length-diameter ratio of 800-1500.
Claims (4)
1. A preparation method of high-length-diameter ratio nanocellulose is characterized in that wood fibers with the concentration of 2-5% are treated for 12-48 hours by composite biological enzyme with the addition amount of 50-150 ppm relative to the absolute dry weight of the wood fibers under the conditions that the temperature is 25-50 ℃ and the pH value is 6.5-8.5, and the composite biological enzyme is formed by compounding endoglucanase, exoglucanase and beta-glucosidase according to the proportion of 10-30: 5-20: 1-5; diluting the treated pulp with water to a concentration of 1.5-2.5 w%, pulping with a pulping machine until the pulping degree is 65-95 DEG SR, adding 0.1-1 w per thousand of dispersing agent or mineral matter with a ground particle diameter of 10-200nm into the obtained pulp according to the absolute dry weight of the wood fiber, and performing colloid mill circulation treatment for 2-10 times, wherein the grinding disc gap is continuously reduced along with the increase of the circulation times, so that the high-length-diameter ratio nano-cellulose with the length-diameter ratio of 500-2000 is obtained.
2. The method of claim 1, wherein the lignocellulose is selected from softwood pulp, hardwood pulp, and bamboo pulp.
3. The method of claim 1, wherein the dispersant is polyethylene oxide (PEO) or Polyacrylamide (PAM).
4. The method of claim 1, wherein the mineral is one or more of talc, kaolin, and titanium dioxide.
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| CN1335856A (en) * | 1999-02-10 | 2002-02-13 | 赫尔克里士公司 | Derivatized microfibrillar polysaccharide |
| JP2012036034A (en) * | 2010-08-05 | 2012-02-23 | Kawaken Fine Chem Co Ltd | Alumina molded article, burned alumina molded article, and method for manufacturing them |
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| CN106988137A (en) * | 2017-04-25 | 2017-07-28 | 华南理工大学 | A kind of clean preparation method of higher concentration nano-cellulose fibril |
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| US8815780B2 (en) * | 2012-02-09 | 2014-08-26 | Ut-Battelle, Llc | Platform for immobilization and observation of subcellular processes |
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| CN1335856A (en) * | 1999-02-10 | 2002-02-13 | 赫尔克里士公司 | Derivatized microfibrillar polysaccharide |
| JP2012036034A (en) * | 2010-08-05 | 2012-02-23 | Kawaken Fine Chem Co Ltd | Alumina molded article, burned alumina molded article, and method for manufacturing them |
| JP2013110987A (en) * | 2011-11-25 | 2013-06-10 | National Institute Of Advanced Industrial Science & Technology | Method of manufacturing cellulose nanofiber |
| WO2015037658A1 (en) * | 2013-09-11 | 2015-03-19 | 日東紡績株式会社 | Cellulose nanofibers, method for producing same, aqueous dispersion using cellulose nanofibers, and fiber-reinforced composite material |
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