CN103174046B - A kind of acid hydrolysis and ultrasonic process coordinate system are for the method for nano micro crystal cellulose - Google Patents
A kind of acid hydrolysis and ultrasonic process coordinate system are for the method for nano micro crystal cellulose Download PDFInfo
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Abstract
The invention discloses a kind of acid hydrolysis and the ultrasonic process coordinate system method for nano micro crystal cellulose.Its method is the certain density sulfuric acid solution of preparation, and lentamente the tonnor EM100 powder provided by Shanghai Tonnor Material Science Co., Ltd. is added in sulfuric acid solution while stirring, ultrasonic process certain hour again after tonnor EM100 powder dissolves completely, a certain amount of distilled water cessation reaction is added after ultrasonic process, the mixed liquor obtained carries out centrifugation, by the Nanocrystalline Cellulose Colloid collected dialysis until be neutral, finally obtain nano micro crystal cellulose powder through refrigeration and freeze drying successively.Should method simple to operate, to cellulose degradation not damaged and more easy to control; Importantly compare with simple acid hydrolysis, can environmental pollution be reduced.
Description
Technical field
That the present invention relates to is a kind of preparation method of nano micro crystal cellulose.This invention be the TONNOR EM100 powder that provides with Shanghai Tonnor Material Science Co., Ltd. for raw material, sulfuric acid is reaction acid, adopts the method for acid hydrolysis and supersonic synergic to obtain nano micro crystal cellulose.
Background technology
In the world today, the energy consumes fast, under the severe situation of ecological deterioration, exploitation regenerative resource has its own strategic significance.Cellulose as a kind of very abundant reproducible Green Polymer Material of occurring in nature, one of target becoming human research.Such as, but it exists some shortcoming in performance, not resistance to chemical attack, low-intensity etc., its physical aspect also limits its range of application.If but were prepared into nano micro crystal cellulose, just could optimize its performance to a great extent, make it have more wide range of application.Because nano micro crystal cellulose not only has cellulosic basic structure and performance, there are again some characteristics of nanoparticle simultaneously, the optical property of such as huge specific area, high-crystallinity, high-hydrophilic, high-modulus, high strength, hyperfine structure and excellence.In view of the premium properties of its uniqueness, it is widely used in fields such as fine chemistry industry, medicine, food, ultra micro composite, heat exchange material and new forms of energy.So the preparation of nano micro crystal cellulose is significant.
At present, the topmost preparation method of nano micro crystal cellulose is acid-hydrolysis method, the nano micro crystal cellulose that acid-hydrolysis method obtains maintains the original crystal formation of cellulose, wherein sulfuric acid is topmost acid, the nano micro crystal cellulose prepared of sulphuric acid hydrolysis because a large amount of sulfonic acid group and electronegative is introduced on surface, can stable dispersion in water.But the environmental pollution that acid-hydrolysis method brings becomes the bottleneck of restriction nano micro crystal cellulose exploitation.Therefore, research and develop a kind of green, efficient, controlled nano micro crystal cellulose preparation method is urgent problem.
Summary of the invention
For this problem, the object of this invention is to provide the new method that a kind of acid hydrolysis and supersonic synergic obtain nano-cellulose.Sulphuric acid hydrolysis ensure that cellulosic crystal formation in nano micro crystal cellulose raw material and can make nano-cellulose stable dispersion in water, and ultrasonic adds minimizing environmental pollution, and whole experimentation is easy to operate controlled.
The object of the invention is to be achieved through the following technical solutions:
One, sulphuric acid hydrolysis works in coordination with ultrasonic process cellulose: first join in distilled water by the concentrated sulfuric acid, be mixed with the sulfuric acid solution that mass concentration is 55% ~ 70%, sulfuric acid solution to be diluted is cooled to room temperature, low whipping speed is for slowly adding the TONNOR EM100 powder provided by Shanghai Tonnor Material Science Co., Ltd. while 200r/min ~ 600r/min stirring, mix rear beginning timing, after reaction 60min ~ 120min, be 90W ~ 1600W by homogeneous mixture at power again, temperature is in the ultrasonic cleaning machine of 35 DEG C ~ 65 DEG C after ultrasonic process 5min ~ 15h, add water cessation reaction, obtain acid hydrolysis and the standby nano micro crystal cellulose mixed liquor of ultrasonic process coordinate system.
Two, the preparation of Nanocrystalline Cellulose Colloid: first by the acid hydrolysis obtained in step one and ultrasonic process coordinate system standby nano micro crystal cellulose mixed liquor is set to 10000r/min ~ 13000r/min at rotating speed, set of time is centrifugation in the centrifuge of 5min ~ 15min, Nanocrystalline Cellulose Colloid can be collected complete centrifugal 2 ~ 8 times, the bag filter dialysis 2 ~ 3 days that specification is 8000 ~ 14000 is placed in by collecting the Nanocrystalline Cellulose Colloid that obtains, dislysate is distilled water, finally obtains neutral Nanocrystalline Cellulose Colloid.
Three, freeze drying: the neutral Nanocrystalline Cellulose Colloid obtained in step 2 is refrigerated 20 days ~ 35 days at temperature 2 DEG C ~ 8 DEG C, there is not lamination, namely Nanocrystalline Cellulose Colloid can stable existence, finally by the freeze drying in freeze drier of stable Nanocrystalline Cellulose Colloid, namely obtain Powdered nano micro crystal cellulose.
Wherein in step one, TONNOR EM100 powder quality and sulfuric acid volume ratio are 1:(4 ~ 12), namely solid-to-liquid ratio is 1:(4 ~ 12); In step 2, each centrifuge washing adding distil water amount is 25ml ~ 35ml.
Advantage of the present invention: one, collaborative ultrasonic process in the process of acidolysis, ultrasonic mechanical effect can open cellulose microcellular structure, improve cellulose template hole to the visibility of sulfuric acid molecule and chemical reactivity, ultrasonic cavitation makes the amorphous region of microcrystalline cellulose destroyed and is refined as nano micro crystal cellulose simultaneously, compared with the method preparing nano-cellulose with sulphuric acid hydrolysis, the method yield that nano-cellulose is prepared in ultrasonic wave added acid hydrolysis significantly improves; Two, sulphuric acid hydrolysis ensure that the nano micro crystal cellulose of preparation keeps cellulosic crystal formation in raw material, and the introducing of sulfonic acid group makes nano micro crystal cellulose stable dispersion in water, can preserve for a long time; Three, preparation technology's flow process is simple, and easy to operate and control.
Accompanying drawing explanation
Fig. 1 is the situation of change of yield with different ultrasonic time of nano micro crystal cellulose prepared by acid hydrolysis and supersonic synergic process.
Detailed description of the invention
Embodiment 1:
One, sulphuric acid hydrolysis cellulose: first the concentrated sulfuric acid is joined in distilled water, be mixed with the sulfuric acid solution that mass concentration is 65%, sulfuric acid solution to be diluted is cooled to room temperature, low whipping speed is 300r/min, temperature slowly adds the TONNOR EM100 powder provided by Shanghai Tonnor Material Science Co., Ltd. while 50 DEG C, mix rear beginning timing, after reaction 120min, add water cessation reaction, obtains nano micro crystal cellulose mixed liquor prepared by acid hydrolysis.Two, the preparation of Nanocrystalline Cellulose Colloid: it is centrifugation in the centrifuge of 10min that the nano micro crystal cellulose the mixed liquor first acid hydrolysis obtained in step one prepared is set to 11000 r/min set of times at rotating speed, Nanocrystalline Cellulose Colloid can be collected complete centrifugal 3 ~ 6 times, the bag filter dialysis 2 ~ 3 days that specification is 8000 ~ 14000 is placed in by collecting the Nanocrystalline Cellulose Colloid that obtains, dislysate is distilled water, finally obtains neutral Nanocrystalline Cellulose Colloid.Three, freeze drying: the neutral Nanocrystalline Cellulose Colloid obtained in step 2 is refrigerated 25 days at temperature 6 DEG C, there is not lamination, namely Nanocrystalline Cellulose Colloid can stable existence, finally by the freeze drying in freeze drier of stable Nanocrystalline Cellulose Colloid, namely obtain Powdered nano micro crystal cellulose.In this implementation step one, TONNOR EM100 powder quality and sulfuric acid volume ratio are 1:10; In step 2, each centrifuge washing adding distil water amount is 25ml ~ 35ml.The yield of nano micro crystal cellulose prepared by the present embodiment is 33.00%.
Embodiment 2:
One, sulphuric acid hydrolysis works in coordination with ultrasonic process cellulose: first join in distilled water by the concentrated sulfuric acid, be mixed with the sulfuric acid solution that mass concentration is 65%, sulfuric acid solution to be diluted is cooled to room temperature, low whipping speed is 300r/min, temperature slowly adds the TONNOR EM100 powder provided by Shanghai Tonnor Material Science Co., Ltd. while 50 DEG C, mix rear beginning timing, after reaction 110min, be in the ultrasonic cleaning machine of 100W after ultrasonic 10min at power, add water cessation reaction, obtain acid hydrolysis and the standby nano micro crystal cellulose mixed liquor of ultrasonic process coordinate system.Two, the preparation of Nanocrystalline Cellulose Colloid: first the acid hydrolysis obtained in step one and the standby nano micro crystal cellulose mixed liquor of ultrasonic process coordinate system being set to 11000 r/min set of times at rotating speed is centrifugation in the centrifuge of 10min, Nanocrystalline Cellulose Colloid can be collected complete centrifugal 3 ~ 6 times, the bag filter dialysis 2 days ~ 3 days that specification is 8000 ~ 14000 is placed in by collecting the Nanocrystalline Cellulose Colloid that obtains, dislysate is distilled water, finally obtains neutral Nanocrystalline Cellulose Colloid.Three, freeze drying: the neutral Nanocrystalline Cellulose Colloid obtained in step 2 is refrigerated 25 days at temperature 6 DEG C, there is not lamination, namely Nanocrystalline Cellulose Colloid can stable existence, finally by the freeze drying in freeze drier of stable Nanocrystalline Cellulose Colloid, namely obtain Powdered nano micro crystal cellulose.In this implementation step one, TONNOR EM100 powder quality and sulfuric acid volume ratio are 1:10; In step 2, each centrifuge washing adding distil water amount is 25ml.The yield of nano micro crystal cellulose prepared by the present embodiment is about 33.55%.
Embodiment 3:
One, sulphuric acid hydrolysis works in coordination with ultrasonic process cellulose: first join in distilled water by the concentrated sulfuric acid, be mixed with the sulfuric acid solution that mass concentration is 65%, sulfuric acid solution to be diluted is cooled to room temperature, low whipping speed is 300r/min, temperature slowly adds the TONNOR EM100 powder provided by Shanghai Tonnor Material Science Co., Ltd. while 50 DEG C, mix rear beginning timing, after reaction 100min, be in the ultrasonic cleaning machine of 100W after ultrasonic 20min at power, add water cessation reaction, obtain acid hydrolysis and the standby nano micro crystal cellulose mixed liquor of ultrasonic process coordinate system.Add water cessation reaction, obtains acid hydrolysis and the standby nano micro crystal cellulose mixed liquor of ultrasonic process coordinate system.Two, the preparation of Nanocrystalline Cellulose Colloid: first the acid hydrolysis obtained in step one and the standby nano micro crystal cellulose mixed liquor of ultrasonic process coordinate system being set to 11000 r/min set of times at rotating speed is centrifugation in the centrifuge of 10min, Nanocrystalline Cellulose Colloid can be collected complete centrifugal 3 ~ 6 times, the bag filter dialysis 2 ~ 3 days that specification is 8000 ~ 14000 is placed in by collecting the Nanocrystalline Cellulose Colloid that obtains, dislysate is distilled water, finally obtains neutral Nanocrystalline Cellulose Colloid.Three, freeze drying: the neutral Nanocrystalline Cellulose Colloid obtained in step 2 is refrigerated 25 days at temperature 6 DEG C, there is not lamination, namely Nanocrystalline Cellulose Colloid can stable existence, finally by the freeze drying in freeze drier of stable Nanocrystalline Cellulose Colloid, namely obtain Powdered nano micro crystal cellulose.In this implementation step one, TONNOR EM100 powder quality and sulfuric acid volume ratio are 1:10; In step 2, each centrifuge washing adding distil water amount is 25ml ~ 35ml.The yield of nano micro crystal cellulose prepared by the present embodiment is about 35.00%.
Embodiment 4:
One, sulphuric acid hydrolysis works in coordination with ultrasonic process cellulose: first join in distilled water by the concentrated sulfuric acid, be mixed with the sulfuric acid solution that mass concentration is 65%, sulfuric acid solution to be diluted is cooled to room temperature, low whipping speed is 300r/min, temperature slowly adds the TONNOR EM100 powder provided by Shanghai Tonnor Material Science Co., Ltd. while 50 DEG C, mix rear beginning timing, after reaction 90min, be in the ultrasonic cleaning machine of 100W after ultrasonic 30min at power, add water cessation reaction, obtain acid hydrolysis and the standby nano micro crystal cellulose mixed liquor of ultrasonic process coordinate system.Add water cessation reaction, obtains acid hydrolysis and the standby nano micro crystal cellulose mixed liquor of ultrasonic process coordinate system.Two, the preparation of Nanocrystalline Cellulose Colloid: first the acid hydrolysis obtained in step one and the standby nano micro crystal cellulose mixed liquor of ultrasonic process coordinate system being set to 11000 r/min set of times at rotating speed is centrifugation in the centrifuge of 30min, Nanocrystalline Cellulose Colloid can be collected complete centrifugal 3 ~ 6 times, the bag filter dialysis 2 days ~ 3 days that specification is 8000 ~ 14000 is placed in by collecting the Nanocrystalline Cellulose Colloid that obtains, dislysate is distilled water, finally obtains neutral Nanocrystalline Cellulose Colloid.Three, freeze drying: the neutral Nanocrystalline Cellulose Colloid obtained in step 2 is refrigerated 25 days at temperature 6 DEG C, there is not lamination, namely Nanocrystalline Cellulose Colloid can stable existence, finally by the freeze drying in freeze drier of stable Nanocrystalline Cellulose Colloid, namely obtain Powdered nano micro crystal cellulose.In this implementation step one, TONNOR EM100 powder quality and sulfuric acid volume ratio are 1:10; In step 2, each centrifuge washing adding distil water amount is 25ml ~ 35ml.The yield of nano micro crystal cellulose prepared by the present embodiment is about 40.43%.
Embodiment 5:
One, sulphuric acid hydrolysis works in coordination with ultrasonic process cellulose: first join in distilled water by the concentrated sulfuric acid, be mixed with the sulfuric acid solution that mass concentration is 65%, sulfuric acid solution to be diluted is cooled to room temperature, low whipping speed is 300r/min, temperature slowly adds the TONNOR EM100 powder provided by Shanghai Tonnor Material Science Co., Ltd. while 50 DEG C, mix rear beginning timing, after reaction 80min, be in the ultrasonic cleaning machine of 100W after ultrasonic 40min at power, add water cessation reaction, obtain acid hydrolysis and the standby nano micro crystal cellulose mixed liquor of ultrasonic process coordinate system.Add water cessation reaction, obtains acid hydrolysis and the standby nano micro crystal cellulose mixed liquor of ultrasonic process coordinate system.Two, the preparation of Nanocrystalline Cellulose Colloid: first the acid hydrolysis obtained in step one and the standby nano micro crystal cellulose mixed liquor of ultrasonic process coordinate system being set to 11000 r/min set of times at rotating speed is centrifugation in the centrifuge of 10min, Nanocrystalline Cellulose Colloid can be collected complete centrifugal 3 ~ 6 times, the bag filter dialysis 2 days ~ 3 days that specification is 8000 ~ 14000 is placed in by collecting the Nanocrystalline Cellulose Colloid that obtains, dislysate is distilled water, finally obtains neutral Nanocrystalline Cellulose Colloid.Three, freeze drying: the neutral Nanocrystalline Cellulose Colloid obtained in step 2 is refrigerated 25 days at temperature 6 DEG C, there is not lamination, namely Nanocrystalline Cellulose Colloid can stable existence, finally by the freeze drying in freeze drier of stable Nanocrystalline Cellulose Colloid, namely obtain Powdered nano micro crystal cellulose.In this implementation step one, TONNOR EM100 powder quality and sulfuric acid volume ratio are 1:10; In step 2, each centrifuge washing adding distil water amount is 25ml ~ 35ml.The yield of nano micro crystal cellulose prepared by the present embodiment is about 41.06%.
Embodiment 6:
One, sulfuric acid water is worked in coordination with ultrasonic process and is separated cellulose: first join in distilled water by the concentrated sulfuric acid, be mixed with the sulfuric acid solution that mass concentration is 65%, sulfuric acid solution to be diluted is cooled to room temperature, low whipping speed is 300r/min, temperature slowly adds the TONNOR EM100 powder provided by Shanghai Tonnor Material Science Co., Ltd. while 50 DEG C, mix rear beginning timing, after reaction 70min, be in the ultrasonic cleaning machine of 100W after ultrasonic 50min at power, add water cessation reaction, obtain acid hydrolysis and the standby nano micro crystal cellulose mixed liquor of ultrasonic process coordinate system.Add water cessation reaction, obtains acid hydrolysis and the standby nano micro crystal cellulose mixed liquor of ultrasonic process coordinate system.Two, the preparation of Nanocrystalline Cellulose Colloid: first the acid hydrolysis obtained in step one and the standby nano micro crystal cellulose mixed liquor of ultrasonic process coordinate system being set to 11000 r/min set of times at rotating speed is centrifugation in the centrifuge of 10min, Nanocrystalline Cellulose Colloid can be collected complete centrifugal 3 ~ 6 times, the bag filter dialysis 2 days ~ 3 days that specification is 8000 ~ 14000 is placed in by collecting the Nanocrystalline Cellulose Colloid that obtains, dislysate is distilled water, finally obtains neutral Nanocrystalline Cellulose Colloid.Three, freeze drying: the neutral Nanocrystalline Cellulose Colloid obtained in step 2 is refrigerated 25 days at temperature 6 DEG C, there is not lamination, namely Nanocrystalline Cellulose Colloid can stable existence, finally by the freeze drying in freeze drier of stable Nanocrystalline Cellulose Colloid, namely obtain Powdered nano micro crystal cellulose.In this implementation step one, TONNOR EM100 powder quality and sulfuric acid volume ratio are 1:10; In step 2, each centrifuge washing adding distil water amount is 25ml ~ 35ml.The yield of nano micro crystal cellulose prepared by the present embodiment is about 41.56%.
Embodiment 1 ~ 6 shows, the yield of the nano micro crystal cellulose prepared by acid hydrolysis and ultrasonic process Synergistic method is increased along with the increase of ultrasonic time, but ultrasonic time is more than 30min, nano micro crystal cellulose yield increases not obvious (see figure 1), consider economic benefit, ultrasonic time selects 30min more suitable.The concrete time depends on ultrasonic power, raw materials etc.Therefore must determine according to concrete preparation method's test, Best Times provided by the invention only plays directive function.
Although embodiment of the present invention are open as above, but it is not restricted to listed in description and embodiment utilization, 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.
This patent to other raw materials, as paper pulp, lumber fibre, agriculture and forestry organic waste material (as stalk, bagasse etc.) adopt this patent method to prepare NCC and also protect.
Claims (7)
1. acid hydrolysis and ultrasonic process coordinate system are for a method for nano micro crystal cellulose, it is characterized in that the method comprises the steps:
Step one, sulphuric acid hydrolysis works in coordination with ultrasonic process cellulose: first join in distilled water by the concentrated sulfuric acid, be mixed with the sulfuric acid solution that mass concentration is 55% ~ 70%, sulfuric acid solution to be diluted is cooled to room temperature, low whipping speed is for slowly adding the TONNOR EM100 powder provided by Shanghai Tonnor Material Science Co., Ltd. while 200r/min ~ 600r/min stirring, mix rear beginning timing, after reaction 60min ~ 120min, again by homogeneous mixture at power 90W ~ 1600W, temperature is in the ultrasonic cleaning machine of 35 DEG C ~ 65 DEG C after ultrasonic process 5min ~ 15h, add water cessation reaction, obtain acid hydrolysis and the standby nano micro crystal cellulose mixed liquor of ultrasonic process coordinate system,
The preparation of step 2, Nanocrystalline Cellulose Colloid: first by the acid hydrolysis obtained in step one and ultrasonic process coordinate system standby nano micro crystal cellulose mixed liquor is set to 10000r/min ~ 13000r/min at rotating speed, set of time is centrifugation in the centrifuge of 5min ~ 15min, Nanocrystalline Cellulose Colloid can be collected complete centrifugal 2 ~ 8 times, the bag filter dialysis 2 days ~ 3 days that specification is 8000 ~ 14000 is placed in by collecting the Nanocrystalline Cellulose Colloid that obtains, dislysate is distilled water, finally obtains neutral Nanocrystalline Cellulose Colloid;
Step 3, freeze drying: by the Nanocrystalline Cellulose Colloid freeze drying in freeze drier obtained in step 2, namely obtain Powdered nano micro crystal cellulose.
2. a kind of acid hydrolysis according to claim 1 and ultrasonic process coordinate system are for the method for nano micro crystal cellulose, it is characterized in that: in step one, TONNOR EM100 powder quality and sulfuric acid volume ratio are 1:4 ~ 12, and namely solid-to-liquid ratio is 1:4 ~ 12; Sulfuric acid concentration is 59% ~ 65%.
3. a kind of acid hydrolysis according to claim 1 and ultrasonic process coordinate system are for the method for nano micro crystal cellulose, it is characterized in that: the acid hydrolysis low whipping speed described in step one is 300r/min ~ 500r/min, temperature is carry out in the water-bath of 40 DEG C ~ 60 DEG C.
4. a kind of acid hydrolysis according to claim 1 and ultrasonic process coordinate system are for the method for nano micro crystal cellulose, it is characterized in that: first to carry out after acid hydrolysis 70min ~ 110min ultrasonic process 10min ~ 12h again described in step one.
5. a kind of acid hydrolysis according to claim 1 and ultrasonic process coordinate system are for the method for nano micro crystal cellulose, it is characterized in that: the ultrasonic power described in step one be 100W ~ 1500W, ultrasonic time temperature be 40 DEG C ~ 60 DEG C.
6. a kind of acid hydrolysis according to claim 1 and ultrasonic process coordinate system are for the method for nano micro crystal cellulose, it is characterized in that: the Nanocrystalline Cellulose Colloid described in step 2 is in the centrifuge of 11000r/min ~ 12000 r/min at rotating speed, centrifugation 6min ~ 10min, centrifugal 3 ~ 6 times.
7. a kind of acid hydrolysis according to claim 1 and ultrasonic process coordinate system are for the method for nano micro crystal cellulose, it is characterized in that: the neutral Nanocrystalline Cellulose Colloid described in step 3 refrigerates 25 days ~ 30 days at temperature 4 DEG C ~ 6 DEG C.
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