CN102911274B - Method for chemically preparing nano microcrystalline cellulose by utilizing moso bamboo - Google Patents
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- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 4
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Abstract
The invention discloses a method for chemically preparing nano microcrystalline cellulose by utilizing moso bamboo. The adopted method has key points that the moso bamboo is respectively subjected to alkali solution treatment and chlorine-containing solution treatment to purify cellulose, moso bamboo fibers are catalyzed and hydrolyzed by adopting an organic acid and a moso bamboo nano microcrystalline cellulose product is collected by virtue of an ultrafiltration membrane. The method disclosed by the invention is rapid and efficient and is especially applicable to preparation of nano microcrystalline cellulose by adopting the moso bamboo raw material. According to the method disclosed by the invention, a moso bamboo resource is introduced into a fiber raw material used for preparing the nano microcrystalline cellulose, the range of the raw material used for preparing the nano microcrystalline cellulose is expanded, rapid break-through of limitation of source of the raw material of the nano microcrystalline cellulose can be facilitated, and an innovative thinking is provided for high-valued utilization of the moso bamboo resource, so that economic income of peasant in bamboo regions in China can be reliably increased, and the method disclosed by the invention has practical significance.
Description
Technical field
The present invention relates to a kind of method of preparing nano micro crystal cellulose, particularly a kind of method of utilizing mao bamboon chemical preparation nano micro crystal cellulose, belongs to Pulp and Paper Engineering field.
Background technology
Mierocrystalline cellulose is the abundantest natural high moleculer eompound of content on the earth, is formed by connecting by β-Isosorbide-5-Nitrae-glycosidic link chain by single D-Glucose unit.Nano micro crystal cellulose is the levelling-off DP solid product with nanoscale and excellent performance being obtained through glass-ceramic process by natural cellulose.Nano micro crystal cellulose not only has basic structure and the performance of general fibre element, also possesses the characteristic of nano particle, as huge specific surface area, higher Young's modulus, superpower adsorptive power and sensitive reactive behavior, there is larger difference in its character and general fibre element.Nano micro crystal cellulose has more reactive group than general fibre element, and chemical reactivity is large, can be used for efficient cellulose chemistry modification.
But at present, the limitation of raw materials almost becomes " bottleneck " that obstruction nano micro crystal cellulose commercially produced product is come out of the stove.The natural matter that present stage is prepared nano micro crystal cellulose employing is mainly linters, wood pulp and tunicin.There is comparatively small amt, extract the problems such as inconvenience in tunicin; Linters, because its content of cellulose can reach more than 90%, can be used as the high-quality fibrous material of preparing nano micro crystal cellulose, but has raw material supplying and the problem such as expensive; Wood raw material, can be for the preparation of nano micro crystal cellulose after special processing treatment, but the growth cycle of lignocellulose raw material is relatively long.In nano micro crystal cellulose preparation field, Chinese patent (ZL 00117261.1) " a kind of nano micro crystal cellulose and method for making " is take linters as raw material, the mixture of one or more in employing sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid, or the mixture of one or more in employing vinylformic acid, phenylformic acid, oxalic acid, or adopt solid acid hydrolysis to prepare nano micro crystal cellulose, and its pattern and crystal formation are characterized; Chinese patent (ZL 01107523.6) " a kind of nano micro crystal cellulose and method for making with cellulose Ⅱ crystal formation " is take linters as raw material, adopt DMSO and highly basic simultaneously swelling, nano micro crystal cellulose has been prepared in mineral acid, organic acid or solid peracid hydrolysis, and has described its pattern and crystalline structure; Chinese patent (ZL200510100343.6) " is prepared the method for nano micro crystal cellulose " take sisal fibers or lumber fibre as raw material with chlorine oxidation degradation, adopt chlorine oxidation degradation to prepare the pure white spherical nano micro crystal cellulose of color and luster; It is raw material that United States Patent (USP) (US20100124651A1) " Method of manufacturing nano-crystalline cellulose film " adopts lumber fibre nano micro crystal cellulose, with organic compound with inorganic materials, prepare high-strength nano composite material film, significantly improved the physicals of former film; The nano micro crystal cellulose that United States Patent (USP) (US 008105430B2) " Aircraft anti-icing fluids formulated withnanocrystalline cellulose " is originated using lumber fibre is as thickening material, be mixed with chemical machine auxiliary agent, prepare the anti-icing compositions of aircraft, for promoting the freezing performance that prevents of aircraft skin.So far, yet there are no and utilize mao bamboon as the Mierocrystalline cellulose thing of originating, occur in order to the related process technology of preparing nano micro crystal cellulose.
Mao bamboon is the most important Economic Bamboo kind of China, and approximately 3,400,000 hectares of cultivated areas, account for 68% of national bamboo grove area, and the mao bamboon bamboo grove area of Zhejiang, Fujian, Jiangxi San Sheng accounts for the over half of the whole nation, is China's mao bamboon emphasis producing region.Mao bamboon has become the important sources of China's bamboo district peasant economy income.Mao bamboon belongs to rank vegetation resource, has fast growth, the cycle of becoming a useful person is short, fibre content advantages of higher, and its fibre shape and fibrocyte content approach even higher than general leaf wood.How to make full use of the bamboo resource of China's abundant, the renewable nanometer novel material of preparation high added value, becomes practical raising China bamboo district peasant economy income, opens one's minds for one of higher value application bamboo resource simultaneously, meet national development circular economy policy, therefore have important practical significance.
Summary of the invention
Prepare at present the problems such as the fibrous material undersupply of nano micro crystal cellulose, expensive, growth cycle be long in order to overcome, the bamboo resource of recycling China's abundant simultaneously, with the renewable nanometer novel material of preparation high added value, the object of this invention is to provide a kind of method of utilizing mao bamboon chemical preparation nano micro crystal cellulose.
For achieving the above object, technical scheme of the present invention is to adopt following steps:
1) by mao bamboon defoliation, clean, dry, adopt plant pulverizer to pulverize, filter through 100 eye mesh screens, obtain the mao bamboon powder that particle diameter is less than or equal to 0.15mm;
2) by the mao bamboon powder obtaining in step 1) under mechanical agitation, in 70 ~ 90 ℃ of basic solutions, react 90 ~ 120min, repeat 3 times, clean residual alkali with distilled water therebetween, obtain mao bamboon fiber;
3) adopt containing chlorine solution under mechanical agitation 60 ~ 80 ℃ of bleaching steps 2) in mao bamboon fiber 150 ~ 210min of obtaining, repeats 4 times, clean residual chlorine with distilled water therebetween, acquisition high purity mao bamboon fiber;
4) by the high purity mao bamboon fiber obtaining in step 3) under mechanical agitation, be placed in 40 ~ 60 ℃ of organic acid solns and react 120 ~ 180min, adopt the room temperature distilled water termination reaction of 5 times of above-mentioned organic acid soln volumes, clean residual acid, obtain mao bamboon nano micro crystal cellulose suspension;
5) by the mao bamboon nano micro crystal cellulose suspension centrifugation 8 ~ 15min under 10000rpm obtaining in step 4), remove solid particulate more than 1 μ m, take out centrifugate through ultrafiltration membrance filter, collect with distilled water the solid ingredient that face is held back, finally obtain mao bamboon nano micro crystal cellulose.
Described basic solution is Mg (OH)
2solution, massfraction is 4.0 ~ 6.0wt%, mao bamboon powder and Mg (OH)
2the mass ratio of solution is 1:5 ~ 10; Be Ca (ClO) containing chlorine solution
2solution, massfraction is 1.5 ~ 3.0wt%, mao bamboon fiber and Ca (ClO)
2the mass ratio of solution is 1:10 ~ 20; Organic acid soln is the mixing acid of one or several the different proportionings in Phenylsulfonic acid, citric acid, trichoroacetic acid(TCA), trifluoro sulphur formic acid, and massfraction is 30 ~ 50wt%, and the mass ratio of mao bamboon fiber and organic acid soln is 1:10 ~ 20.
Described ultra-filtration membrane is the one in poly (ether sulfone) film, PVDF membrane, regenerated cellulose film, and its molecular weight cut-off is 50 ~ 100kDa.
Compared with background technology, the beneficial effect that the present invention has is:
The present invention introduces bamboo resource in the fibrous material of preparing nano micro crystal cellulose, expand the raw material range of preparing nano micro crystal cellulose, the raw material sources limitation that is conducive to accelerate to break through nano micro crystal cellulose, realizes early nano micro crystal cellulose commercially produced product and comes out of the stove; Open one's minds simultaneously for one that proposes higher value application bamboo resource, meet national development circular economy policy, can conscientiously improve China bamboo district peasant's income.
Accompanying drawing explanation
This accompanying drawing is the field emission scanning electron microscope photo of the mao bamboon nano micro crystal cellulose product prepared of the present invention.
Wherein Fig. 1 is that mao bamboon nano micro crystal cellulose amplifies the photo of 10,000 times.
Fig. 2 is that mao bamboon nano micro crystal cellulose amplifies the photo of 50,000 times.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1:
1) by mao bamboon defoliation, clean, dry, adopt plant pulverizer to pulverize, filter through 100 eye mesh screens, obtain the mao bamboon powder that particle diameter is less than or equal to 0.15mm;
2) by the mao bamboon powder obtaining in step 1) under mechanical agitation, be placed in 80 ℃ of 4.0wt%Mg (OH)
2in solution, react 100min, mao bamboon powder and Mg (OH)
2solution quality, than for 1:5, repeats 3 times, cleans residual alkali therebetween with distilled water, obtains mao bamboon fiber;
3) adopt 1.5wt%Ca (ClO)
2solution under mechanical agitation, 80 ℃ of bleaching steps 2) in the mao bamboon fiber 210min that obtains, mao bamboon fiber and Ca (ClO)
2the mass ratio of solution is 1:10, repeats 4 times, cleans residual chlorine therebetween with distilled water, obtains high purity mao bamboon fiber;
4) by the high purity mao bamboon fiber obtaining in step 3) under mechanical agitation, be placed in 40 ℃ of 30wt% trichoroacetic acid(TCA) solution and react 150min, the mass ratio of mao bamboon fiber and organic acid soln is 1:15, adopt the room temperature distilled water termination reaction of 5 times of above-mentioned trichoroacetic acid(TCA) liquor capacities, clean residual acid, obtain mao bamboon nano micro crystal cellulose suspension;
5) by the mao bamboon nano micro crystal cellulose suspension centrifugation 10min under 10000rpm obtaining in step 4), remove solid particulate more than 1 μ m, taking out centrifugate filters through 100kDa poly (ether-sulfone) ultrafiltration membrane, collect with distilled water the solid ingredient that face is held back, finally obtain mao bamboon nano micro crystal cellulose (a).
Embodiment 2:
1) by mao bamboon defoliation, clean, dry, adopt plant pulverizer to pulverize, filter through 100 eye mesh screens, obtain the mao bamboon powder that particle diameter is less than or equal to 0.15mm;
2) by the mao bamboon powder obtaining in step 1) under mechanical agitation, be placed in 90 ℃ of 4.0wt%Mg (OH)
2in solution, react 90min, mao bamboon powder and Mg (OH)
2solution quality, than for 1:10, repeats 3 times, cleans residual alkali therebetween with distilled water, obtains mao bamboon fiber;
3) adopt 2.0wt%Ca (ClO)
2solution under mechanical agitation, 80 ℃ of bleaching steps 2) in the mao bamboon fiber 180min that obtains, mao bamboon fiber and Ca (ClO)
2the mass ratio of solution is 1:20, repeats 4 times, cleans residual chlorine therebetween with distilled water, obtains high purity mao bamboon fiber;
4) by the high purity mao bamboon fiber obtaining in step 3) under mechanical agitation, be placed in 45 ℃ of 50wt% Phenylsulfonic acid solution and react 180min, the mass ratio of mao bamboon fiber and organic acid soln is 1:10, adopt the room temperature distilled water termination reaction of 5 times of above-mentioned Phenylsulfonic acid liquor capacities, clean residual acid, obtain mao bamboon nano micro crystal cellulose suspension;
5) by the mao bamboon nano micro crystal cellulose suspension centrifugation 8min under 10000rpm obtaining in step 4), remove solid particulate more than 1 μ m, take out centrifugate through 100kDa polyvinylidene fluoride ultrafiltration membrane filtration, collect with distilled water the solid ingredient that face is held back, finally obtain mao bamboon nano micro crystal cellulose (b).
Embodiment 3:
1) by mao bamboon defoliation, clean, dry, adopt plant pulverizer to pulverize, filter through 100 eye mesh screens, obtain the mao bamboon powder that particle diameter is less than or equal to 0.15mm;
2) by the mao bamboon powder obtaining in step 1) under mechanical agitation, be placed in 70 ℃ of 6.0wt%Mg (OH)
2in solution, react 120min, mao bamboon powder and Mg (OH)
2solution quality, than for 1:10, repeats 3 times, cleans residual alkali therebetween with distilled water, obtains mao bamboon fiber;
3) adopt 3.0wt%Ca (ClO)
2solution under mechanical agitation, 60 ℃ of bleaching steps 2) in the mao bamboon fiber 150min that obtains, mao bamboon fiber and Ca (ClO)
2the mass ratio of solution is 1:20, repeats 4 times, cleans residual chlorine therebetween with distilled water, obtains high purity mao bamboon fiber;
4) by the high purity mao bamboon fiber obtaining in step 3) under mechanical agitation, in 60 ℃ of 40wt% citric acids and 30wt% trifluoro sulphur formic acid (volume ratio 1:1) mixing solutions, react 120min, the mass ratio of mao bamboon fiber and organic acid soln is 1:20, adopt the room temperature distilled water termination reaction of 5 times of above-mentioned trifluoro sulphur formic acid solution volumes, clean residual acid, obtain mao bamboon nano micro crystal cellulose suspension;
5) by the mao bamboon nano micro crystal cellulose suspension centrifugation 15min under 10000rpm obtaining in step 4), remove solid particulate more than 1 μ m, take out centrifugate through 50kDa regenerated cellulose ultrafiltration membrance filter, collect with distilled water the solid ingredient that face is held back, finally obtain mao bamboon nano micro crystal cellulose (c).
The appearance and size of three kinds of mao bamboon nano micro crystal celluloses that mensuration embodiment 1,2,3 prepares.Table 1 is the characterization result of the mao bamboon nano micro crystal cellulose appearance and size prepared by embodiment 1,2,3.From data in table 1, adopt mao bamboon nano micro crystal cellulose (a) that preparation method of the present invention obtains, (b), (c) length distribution at 211 ~ 280nm, width distribution is at 15 ~ 24nm, length-to-diameter ratio is between 12 ~ 15, be nano-scale range, meet nano micro crystal cellulose dimensions feature.
As Fig. 1, the field emission scanning electron microscope photo of the mao bamboon nano micro crystal cellulose product of preparing from embodiment 1 can be found out, its pattern is close to bar-shaped, owing to having higher specific surface area and abundant surface hydroxyl, there is slight attracting each other and agglomeration in the mao bamboon nano micro crystal cellulose of preparation.
Table 1
What more than enumerate is only specific embodiments of the invention.The invention is not restricted to above embodiment, can also have many distortion.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (2)
1. a method of utilizing mao bamboon chemical preparation nano micro crystal cellulose, is characterized in that, comprises the following steps:
1) by mao bamboon defoliation, clean, dry, adopt plant pulverizer to pulverize, filter through 100 eye mesh screens, obtain the mao bamboon powder that particle diameter is less than or equal to 0.15mm;
2) by step 1) in the mao bamboon powder that obtains under mechanical agitation, in 70～90 ℃ of basic solutions, react 90～120min, repeat 3 times, clean residual alkali with distilled water therebetween, obtain mao bamboon fiber;
3) adopt containing chlorine solution under mechanical agitation 60～80 ℃ of bleaching steps 2) in mao bamboon fiber 150～210min of obtaining, repeats 4 times, clean residual chlorine with distilled water therebetween, acquisition high purity mao bamboon fiber;
4) by step 3) in the high purity mao bamboon fiber that obtains under mechanical agitation, be placed in 40～60 ℃ of organic acid solns and react 120～180min, adopt the room temperature distilled water termination reaction of 5 times of above-mentioned organic acid soln volumes, clean residual acid, obtain mao bamboon nano micro crystal cellulose suspension;
5) by step 4) in mao bamboon nano micro crystal cellulose suspension centrifugation 8～15min under 10000rpm of obtaining, remove solid particulate more than 1 μ m, take out centrifugate through ultrafiltration membrance filter, collect with distilled water the solid ingredient that face is held back, finally obtain mao bamboon nano micro crystal cellulose;
Described basic solution is Mg (OH)
2solution, massfraction is 4.0～6.0wt%, mao bamboon powder and Mg (OH)
2the mass ratio of solution is 1:5～10; Be Ca (ClO) containing chlorine solution
2solution, massfraction is 1.5～3.0wt%, mao bamboon fiber and Ca (ClO)
2the mass ratio of solution is 1:10～20; Organic acid soln is the mixing acid of one or several the different proportionings in Phenylsulfonic acid, citric acid, trichoroacetic acid(TCA), trifluoro sulphur formic acid, and massfraction is 30～50wt%, and the mass ratio of mao bamboon fiber and organic acid soln is 1:10～20.
2. a kind of method of utilizing mao bamboon chemical preparation nano micro crystal cellulose according to claim 1, it is characterized in that: described ultra-filtration membrane is the one in poly (ether sulfone) film, PVDF membrane, regenerated cellulose film, its molecular weight cut-off is 50～100kDa.
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| CN109485737A (en) * | 2018-12-19 | 2019-03-19 | 国际竹藤中心 | A method of Cellulose nanocrystal is prepared using moso bamboo |
| CN109457524B (en) * | 2018-12-29 | 2023-10-20 | 珠海市东辰制药有限公司 | Purification method and purification equipment of nano microcrystalline cellulose |
| CN110128554A (en) * | 2019-05-22 | 2019-08-16 | 江西农业大学 | A method of nano micro crystal cellulose is prepared using moso bamboo |
| CN111673876A (en) * | 2020-05-29 | 2020-09-18 | 泉州市康洪美傲建材科技有限公司 | Preparation method of high-strength wood composite inorganic particle board |
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