CN102899950A - Method for preparing nano cellulose by simultaneous assistance of ultrasonic waves and microwaves - Google Patents
Method for preparing nano cellulose by simultaneous assistance of ultrasonic waves and microwaves Download PDFInfo
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Abstract
The invention discloses a method for preparing nano cellulose by simultaneous assistance of ultrasonic waves and microwaves, belonging to the field of biomass nano materials. According to the nano material, liquid acid is taken as a catalyst, and the high-efficiency hydrolysis at the amorphous area of cellulose is promoted due to the simultaneous assistance of the ultrasonic waves and microwaves, so that the nano cellulose is rapidly prepared by plant fiber raw materials. The preparation method comprises the steps of acid hydrolysis of plant cellulose, centrifugal recovery of liquid acid and centrifugal separation of nano cellulose. According to the method, the mechanical dispersion action and ultrasonic cavitation effect of the ultrasonic waves, microwave uniform heating effect, catalytic action of the liquid acid and the synergistic effect of the ultrasonic waves and microwaves are utilized sufficiently, and the hydrolytic process of cellulose is enhanced, so that the high-efficiency and rapid preparation of the nano cellulose can be realized. The prepared nano cellulose material can be used for food additives, drug excipients, engineering material additives, specialty paper additives and the like.
Description
Technical field
The present invention relates to the simultaneously auxiliary method for preparing nano-cellulose of a kind of ultrasonic-microwave, belong to the biomass nano Material Field.
Background technology
Nano-cellulose typically refers to the high molecular cellulose that on a certain dimension in space size reaches 1-100 nm.Compare with native cellulose, nano cellulose crystal has many premium properties, such as larger specific area, high-crystallinity, high-hydrophilic, high-modulus, high strength, hyperfine structure and high transparent etc.Therefore, nano-cellulose has good using value at the aspects such as wild phase, tissue engineering bracket and filter medium preparation of food additives, composite.At present, the preparation method of nano-cellulose mainly is divided into three kinds of chemical methods, Physical, bioanalysis.Chemical method is normally take liquid acid or alkali as catalyst, and the hydrolysis by cellulosic material prepares nano-cellulose; Physical mainly is to impel cellulose to become nano level cellulose by heating explosion, homogenizer, the physical method such as high-pressure homogeneous; Biological rule mainly is to utilize bacterium that cellulosic biochemical action is prepared nano-cellulose.In above-mentioned three kinds of methods, the energy consumption rate of Physical is higher, product purity is low; Biological preparation complexity, length consuming time, high, the price of cost; Though chemical method is easy to the surface-modified nano cellulose, but usually need strong acid or highly basic as catalyst, consersion unit is had relatively high expectations, catalyst recovery is also difficult.Therefore, the preparation method who further studies and improve nano-cellulose is the research emphasis in this field still.In recent years, adopt ultrasonic wave to assist and prepare the method for nanofiber by wide coverage through acid hydrolysis.The method is a kind of combination of chemical method and Physical, takes full advantage of hyperacoustic mechanical dispersion, ultrasonic cavitation effect, and the cooperative effect between ultrasonic wave and the acid catalysis, has represented good application prospect.But still there are some defectives in the auxiliary preparation of ultrasonic wave nanofiber, and such as sour large usage quantity, preparation time is also longer, and step is relatively many, mostly also need to carry out high-pressure homogeneous or the acid hydrolysis preliminary treatment to plant fiber material, etc.Therefore, on the auxiliary basis of ultrasonic wave, if adopt further reinforcement technique, overcome or improve the defective of the auxiliary preparation of ultrasonic wave nano-cellulose, then be expected to develop a kind of more efficient, cleaning, energy-conservation nano-cellulose preparation method.In recent years, the development of ultrasonic-microwave associating ancillary technique is swift and violent, particularly the application in chemical reaction, extract and separate field has received the concern of numerous researchers, pertinent literature has also confirmed can produce synergy between the ultrasonic wave and microwave in this associating ancillary technique, can further strengthen chemical process, however its application in preparation biomass nano Material Field rarely seen report also.
Summary of the invention
The object of the present invention is to provide a kind of by the ultrasonic-microwave auxiliary method for preparing nano-cellulose simultaneously.The present invention takes full advantage of hyperacoustic mechanical dispersion effect, ultrasonic cavitation effect, microwave homogeneous heating effect, the catalytic action of liquid acid and the synergy that produces between them, the hydrolytic process of resistant cellulose, thus realize that the efficient, quick of nano-cellulose prepares.
For achieving the above object, the present invention adopts following technical scheme:
A kind of ultrasonic-microwave is the auxiliary method for preparing nano-cellulose simultaneously, and concrete steps are as follows:
1) acid hydrolysis of plant cellulose: take string as raw material, after the liquid acid of mass concentration 10-60% is fully mixed, place ultrasonic-microwave synergistic extraction instrument, assist simultaneously lower hydrolysis 0.5-2.0h at 50-80 ℃ with ultrasonic-microwave, the gained mixture is for subsequent use;
2) the centrifugal recovery of liquid acid: with step 1) gained mixture centrifugation 5-10min under 4000-7000rad/min, the supernatant liquor of collection is aq acid soln, concentrated rear the recycling, and the bottom solid phase is for subsequent use;
3) the bottom solid phase centrifugation of nano-cellulose: with step 2) is mixed with deionized water, and regulates the pH value to neutral, and centrifugation 5-10min under 4000-7000rad/min collects upper phase; Repeat above-mentioned dilution, centrifugation step 2-6 time, merging upper phase is nano-cellulose colloidal solution, obtains white nano-cellulose powder after freeze drying.
The described string of step 1) is a kind of in all kinds of filter paper, wood pulp fibre, the bamboo pulp fiber.
The described liquid acid of step 1) is a kind of in sulfuric acid, phosphoric acid, the hydrochloric acid.
Adjusting pH value to neutrality described in the step 3) is by adding calcium oxide to be adjusted to neutrality.
The technological parameter of the described ultrasonic-microwave of step (1) is: ultrasonic wave 40KHz, 50W; Microwave 2450MHz, 10-800W.
More preferably, the acid hydrolysis of step 1) plant cellulose: take string as raw material, after the liquid acid of mass concentration 30-55% is fully mixed, place ultrasonic-microwave synergistic extraction instrument, assist simultaneously lower hydrolysis 1.0-2.0h at 60-80 ℃ with ultrasonic-microwave, the gained mixture is for subsequent use.
Described nanofiber cellulosic material can be used for food additives, drug excipient, engineering material additive, speciality paper additive etc.
Remarkable advantage of the present invention is: the present invention is the preparation nano-cellulose under ultrasonic-microwave is auxiliary simultaneously, take full advantage of hyperacoustic mechanical dispersion effect, ultrasonic cavitation effect, microwave homogeneous heating effect, the catalytic action of liquid acid and the synergy that produces between them, the hydrolytic process of resistant cellulose, thus realize that the efficient, quick of nano-cellulose prepares.The material nano cellulosic material that makes can be used for food additives, drug excipient, engineering material additive, speciality paper additive etc.
Description of drawings
Fig. 1 is the transmission electron microscope figure of nano-cellulose of the present invention.
Fig. 2 is the X-ray diffraction spectrogram of filter paper raw material of the present invention and nano-cellulose product: a filter paper; The b nano-cellulose.
Fig. 3 is the Fourier transform infrared spectroscopy figure of filter paper raw material of the present invention and nano-cellulose product: a filter paper; The b nano-cellulose.
The specific embodiment
The preparation method of nano-cellulose of the present invention comprises the acid hydrolysis of plant cellulose, the centrifugal recovery of liquid acid, the centrifugation of nano-cellulose; Specifically may further comprise the steps:
1) acid hydrolysis of plant cellulose: getting the 0.5-3.0g sponge is raw material, after mass concentration 10-60%, volume 40-60mL liquid acid are fully mixed, place ultrasonic-microwave synergistic extraction instrument, for subsequent use behind the auxiliary lower hydrolysis 0.5-2.0h simultaneously at 50-80 ℃ and ultrasonic-microwave.
2) the centrifugal recovery of liquid acid: with mixture centrifugation 5-10min under 4000-7000rad/min of step 1), the supernatant liquor of collection is aq acid soln, can be recycled after rotary evaporation anhydrates, and the bottom solid phase is for subsequent use.
3) the solid product centrifugation of nano-cellulose: with step 2) mixes with the 50-200mL deionized water, regulates the pH value to neutral by adding a small amount of CaO, and centrifugation 5-10min under 4000-7000rad/min collects upper phase; Need not to regulate the pH value, repeat above-mentioned dilution, centrifugation step 2-6 time.The upper phase of collecting is milky white nano-cellulose colloidal solution, can get white nano-cellulose powder after freeze drying.
Embodiment 1
A kind of ultrasonic-microwave is the auxiliary method for preparing nano-cellulose simultaneously, may further comprise the steps:
1) acid hydrolysis of plant cellulose: after getting 0.5g filter paper fragment and mass concentration 50%, 40mL sulfuric acid fully mixing, in ultrasonic-microwave combined extraction instrument in 65 ℃ of lower ultrasonic-microwaves (ultrasonic wave: 40KHz, 50W; Microwave: 2450MHz, 10-800W regulate automatically according to establishing temperature) for subsequent use behind the assisted reaction 1.5h simultaneously.
2) the centrifugal recovery of liquid acid: with mixture centrifugation 7min under 6000rad/min of step 1), the supernatant liquor of collection is sulfuric acid solution, can be recycled after rotary evaporation anhydrates, and the bottom solid phase is for subsequent use.
3) the solid product centrifugation of nano-cellulose: with step 2) mixes with the 100mL deionized water, regulates the pH value to neutral by adding a small amount of CaO, and centrifugation 7min under 6000rad/min collects upper phase; Need not to regulate the pH value, repeat above-mentioned dilution, centrifugation step 3 times.The upper phase of collecting is milky white nano-cellulose colloidal solution, can get white nano-cellulose powder after freeze drying.
Embodiment 2
A kind of ultrasonic-microwave is the auxiliary method for preparing nano-cellulose simultaneously, may further comprise the steps:
1) acid hydrolysis of plant cellulose: after getting the 1.5g wood pulp fibre and mass concentration 55%, 50mL phosphoric acid fully mixing, in ultrasonic-microwave combined extraction instrument in 60 ℃ of lower ultrasonic-microwaves (ultrasonic wave: 40KHz, 50W; Microwave: 2450MHz, 10-800W regulate automatically according to establishing temperature) for subsequent use behind the assisted reaction 2.0h simultaneously.
2) the centrifugal recovery of liquid acid: with mixture centrifugation 8min under 5000rad/min of step 1), the supernatant liquor of collection is phosphoric acid solution, can be recycled after rotary evaporation anhydrates, and the bottom solid phase is for subsequent use.
3) the solid product centrifugation of nano-cellulose: with step 2) mixes with the 150mL deionized water, regulates the pH value to neutral by adding a small amount of CaO, and centrifugation 8min under 5000rad/min collects upper phase; Need not to regulate the pH value, repeat above-mentioned dilution, centrifugation step 4 times.The upper phase of collecting is milky white nano-cellulose colloidal solution, can get white nano-cellulose powder after freeze drying.
Embodiment 3
A kind of ultrasonic-microwave is the auxiliary method for preparing nano-cellulose simultaneously, may further comprise the steps:
1) acid hydrolysis of plant cellulose: after getting the 1.0g bamboo pulp fiber and mass concentration 50%, 50mL sulfuric acid fully mixing, in ultrasonic-microwave combined extraction instrument in 70 ℃ of lower ultrasonic-microwaves (ultrasonic wave: 40KHz, 50W; Microwave: 2450MHz, 10-800W regulate automatically according to establishing temperature) for subsequent use behind the assisted reaction 1.0h simultaneously.
2) the centrifugal recovery of liquid acid: with mixture centrifugation 5min under 7000rad/min of step 1), the supernatant liquor of collection is phosphoric acid solution, can be recycled after rotary evaporation anhydrates, and the bottom solid phase is for subsequent use.
3) the solid product centrifugation of nano-cellulose: with step 2) mixes with the 150mL deionized water, regulates the pH value to neutral by adding a small amount of CaO, and centrifugation 5min under 7000rad/min collects upper phase; Repeat above-mentioned dilution, centrifugation step 2 times.The upper phase of collecting is milky white nano-cellulose colloidal solution, can get white nano-cellulose powder after freeze drying.
Embodiment 4
A kind of ultrasonic-microwave is the auxiliary method for preparing nano-cellulose simultaneously, may further comprise the steps:
1) acid hydrolysis of plant cellulose: after getting 3.0g filter paper fragment and mass concentration 30%, 60mL hydrochloric acid fully mixing, in ultrasonic-microwave combined extraction instrument in 80 ℃ of lower ultrasonic-microwaves (ultrasonic wave: 40KHz, 50W; Microwave: 2450MHz, 10-800W regulate automatically according to establishing temperature) for subsequent use behind the assisted reaction 2.0h simultaneously.
2) the centrifugal recovery of liquid acid: with mixture centrifugation 10min under 4000rad/min of step 1), the supernatant liquor of collection is hydrochloric acid solution, can be recycled after rotary evaporation anhydrates, and the bottom solid phase is for subsequent use.
3) the solid product centrifugation of nano-cellulose: with step 2) mixes with the 200mL deionized water, regulates the pH value to neutral by adding a small amount of CaO, and centrifugation 10min under 4000rad/min collects upper phase; Need not to regulate the pH value, repeat above-mentioned dilution, centrifugation step 6 times.The upper phase of collecting is milky white nano-cellulose colloidal solution, can get white nano-cellulose powder after freeze drying.
Embodiment 5
Adopt Japanese JEOL JEM-1010 transmission electron microscope (TEM) that the microscopic appearance of sample is characterized.As shown in Figure 1, nano-cellulose is the beard shape, and diameter and length are comparatively even, and diameter is about 30-50nm, and length is about 200-500nm, and local covering, intersection are netted.This characterization result has confirmed simultaneously ancillary technique of employing ultrasonic-microwave intuitively, can prepare nano-cellulose under can be in lower acid concentration, without feed pretreatment step and the condition of shorter reaction time.The nano-cellulose that the present invention prepares than the ultrasonic wave ancillary technique is more efficient, cleaning, energy-conservation.
Embodiment 6
Adopt Dutch Philip X'Pert Pro MPD X-ray powder diffraction instrument filter paper raw material and nano-cellulose powder to be characterized characteristic ray Co-Ka, the filtering of Ni sheet, accelerating potential 80 Kv, sweep speed 0.2
o/ sec, sweep limits 10
o-90
oAs seen from Figure 2, the X-ray diffraction spectrogram broadly similar of nano-cellulose and filter paper proves that cellulosic crystalline form does not change in preparation process, has still kept the crystal formation feature of cellulose Ⅰ.But the peak width of nano-cellulose diffraction maximum obviously narrows down, and the peak is strong to become large, illustrates that its crystal grain is less.In addition, by the diffraction peak intensity of 002 crystal face and 001 crystal face as can be known, the X ray degree of crystallinity of nano-cellulose increases to 68% by 52% of filter paper raw material.Comprehensive transmission electron microscope picture and X-ray diffraction spectrogram are as can be known, ultrasonic wave, microwave, acid-hydrolyzed cooperative effect mainly are to act on cellulosic part amorphous region, thereby cause cellulosic material peel off, rupture, broken etc., impel cellulosic length and rugosity to be tending towards nano-scale.
Embodiment 7
Adopt the KBr pressed disc method that filter paper raw material and nano-cellulose powder are carried out spectrum analysis (Fig. 3) in the Nicolet of U.S. Thermo electro company 380 type Fourier transform infrared spectrometer, sample quality accounts for 0.7% of compressing tablet quality.3345 cm in the collection of illustrative plates
-1Absworption peak belongs to the characteristic absorption peak of hydroxyl in the cellulose; 2902 cm
-1That corresponding is methylene (-CH
2-) C-H symmetrical stretching vibration absworption peak; 1055 cm
-1Absworption peak belongs to the C of cellulose alcohol-O stretching vibration, and near 1112 and 1160 cm it
-1Acromion belongs to respectively the stretching vibration absworption peak of the C of cellulosic molecule inner ether-O stretching vibration absworption peak and C-C skeleton.At 1429 cm
-1Near the flexural vibrations absworption peak of saturated C-H, 899 cm are arranged
-1Then corresponding to cellulose anomeric carbon (C
1) vibration absorption peak.Compare with filter paper, the absworption peak wave number of nano-cellulose illustrates that without significant change both surface functional group kinds are basically identical, and the intensity of nano-cellulose absworption peak larger be that to contain the surface functional group of horn of plenty more caused because of its high-specific surface area.The auxiliary nano-cellulose of preparing of ultrasonic wave is basically identical in the IR Characterization result of this sample and the document, illustrate that the simultaneously application of ancillary technique of ultrasonic-microwave does not change the surface functional group of nano-cellulose, has just strengthened the forming process of nano-cellulose.
The above only is preferred embodiment of the present invention, and all equalizations of doing according to the present patent application claim change and modify, and all should belong to covering scope of the present invention.
Claims (6)
1. a ultrasonic-microwave is assisted the method for preparing nano-cellulose simultaneously, and it is characterized in that: the concrete steps of described method are as follows:
1) acid hydrolysis of plant cellulose: take string as raw material, after the liquid acid of mass concentration 10-60% is fully mixed, place ultrasonic-microwave synergistic extraction instrument, assist simultaneously lower hydrolysis 0.5-2.0h at 50-80 ℃ with ultrasonic-microwave, the gained mixture is for subsequent use;
2) the centrifugal recovery of liquid acid: with step 1) gained mixture centrifugation 5-10min under 4000-7000rad/min, the supernatant liquor of collection is aq acid soln, concentrated rear the recycling, and the bottom solid phase is for subsequent use;
3) the bottom solid phase centrifugation of nano-cellulose: with step 2) is mixed with deionized water, and regulates the pH value to neutral, and centrifugation 5-10min under 4000-7000rad/min collects upper phase; Repeat above-mentioned dilution, centrifugation step 2-6 time, merging upper phase is nano-cellulose colloidal solution, obtains white nano-cellulose powder after freeze drying.
2. the preparation method of nano-cellulose according to claim 1 is characterized in that: the described string of step 1) is a kind of in all kinds of filter paper, wood pulp fibre, the bamboo pulp fiber.
3. the preparation method of nano-cellulose according to claim 1 is characterized in that: the described liquid acid of step 1) is a kind of in sulfuric acid, phosphoric acid, the hydrochloric acid.
4. the preparation method of nano-cellulose according to claim 1 is characterized in that: adjusting pH value to the neutrality described in the step 3) is by adding calcium oxide to be adjusted to neutrality.
5. the preparation method of nano-cellulose according to claim 1, it is characterized in that: the technological parameter of the described ultrasonic-microwave of step (1) is: ultrasonic wave 40KHz, 50W; Microwave 2450MHz, 10-800W.
6. the preparation method of nano-cellulose according to claim 1, it is characterized in that: the acid hydrolysis of step 1) plant cellulose: take string as raw material, after the liquid acid of mass concentration 30-55% is fully mixed, place ultrasonic-microwave synergistic extraction instrument, assist simultaneously lower hydrolysis 1.0-2.0h at 60-80 ℃ with ultrasonic-microwave, the gained mixture is for subsequent use.
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| CN111410696A (en) * | 2020-05-06 | 2020-07-14 | 闽江学院 | Method for preparing fluorescent nano-cellulose by one-pot method |
| CN111410696B (en) * | 2020-05-06 | 2022-03-08 | 闽江学院 | Method for preparing fluorescent nano-cellulose by one-pot method |
| IT202200007589A1 (en) | 2022-04-15 | 2023-10-15 | Pabif Srl | PROCESS AND APPARATUS FOR THE PRODUCTION OF LEVULINIC ACID FROM CELLULOSE OBTAINED FROM BIOMASS |
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