CN114351488A - Composite-morphology nano-cellulose transparent film based on waste paper and preparation method thereof - Google Patents
Composite-morphology nano-cellulose transparent film based on waste paper and preparation method thereof Download PDFInfo
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- 239000010893 paper waste Substances 0.000 title claims abstract description 235
- 229920002678 cellulose Polymers 0.000 title claims abstract description 146
- 239000001913 cellulose Substances 0.000 title claims abstract description 145
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 64
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000002131 composite material Substances 0.000 claims abstract description 30
- 239000008367 deionised water Substances 0.000 claims abstract description 27
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 27
- 239000002761 deinking Substances 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 239000000725 suspension Substances 0.000 claims description 91
- 229920001046 Nanocellulose Polymers 0.000 claims description 74
- 239000000835 fiber Substances 0.000 claims description 43
- 239000007788 liquid Substances 0.000 claims description 38
- 239000012528 membrane Substances 0.000 claims description 30
- 238000004537 pulping Methods 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 229920001131 Pulp (paper) Polymers 0.000 claims description 20
- 238000007865 diluting Methods 0.000 claims description 18
- 230000007935 neutral effect Effects 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 17
- 238000004108 freeze drying Methods 0.000 claims description 13
- 238000007689 inspection Methods 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 11
- 238000000967 suction filtration Methods 0.000 claims description 11
- 238000003828 vacuum filtration Methods 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- 239000002033 PVDF binder Substances 0.000 claims description 9
- 238000007605 air drying Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000005485 electric heating Methods 0.000 claims description 9
- 238000007667 floating Methods 0.000 claims description 9
- 239000006260 foam Substances 0.000 claims description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 9
- 239000012634 fragment Substances 0.000 claims description 8
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000000502 dialysis Methods 0.000 claims description 2
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 16
- 239000001301 oxygen Substances 0.000 abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 abstract description 16
- 230000004888 barrier function Effects 0.000 abstract description 9
- 238000004806 packaging method and process Methods 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 description 15
- 239000000123 paper Substances 0.000 description 13
- 238000007664 blowing Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 6
- 238000004064 recycling Methods 0.000 description 5
- 235000010980 cellulose Nutrition 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000002121 nanofiber Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 229910020489 SiO3 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/64—Paper recycling
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- Polysaccharides And Polysaccharide Derivatives (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a waste paper-based composite-morphology nano-cellulose transparent film, which comprises the following components in percentage by weight: 1.59 to 1.97 percent of waste paper, 31.86 to 39.29 percent of deionized water, 0 to 0.38 percent of deinking agent and 58.52 to 66.14 percent of concentrated sulfuric acid with the mass fraction of 98 percent, wherein the sum of the weight percentages of the components is 100 percent. The transparent film has high crystallinity, good thermal property and oxygen barrier property, and has wide application prospect in the fields of packaging and the like. Also discloses a preparation method of the composite morphology nano-cellulose transparent film based on the waste paper.
Description
Technical Field
The invention belongs to the field of waste recycling and nano material extraction and preparation, and particularly relates to a waste paper-based composite-morphology nano cellulose transparent film and a preparation method thereof.
Background
More than four hundred million tons of waste paper are produced in the world every year, the quantity of the waste paper is large, but the recovery rate is low, a considerable part of the waste paper is still treated by landfill or incineration, huge pressure is brought to the environment, only about 50% -65% of the waste paper is recovered, the recovery and utilization way is single, most of the waste paper is used for producing recycled paper, the added value of products is low, and the resource waste is caused invisibly. Therefore, a new way for realizing high-quality recycling of the waste paper is sought, and the method has important practical significance and social benefit.
The waste paper contains a large amount of cellulose, has the characteristics of rich sources, low price and the like, and is an excellent cellulose resource. Based on a new concept of green development, the waste paper is utilized to produce the widely applied nano-cellulose, so that the waste of paper resources can be reduced, the environmental protection is facilitated, the reasonable utilization of the resources is realized, and the recycling approach of the waste paper is further developed. The film material has become a hotspot of current research, the film material prepared by taking cellulose as a raw material has good application prospect in the field of packaging, plays an important role in production and life, and has important significance for developing green chemistry and promoting human sustainable development.
Disclosure of Invention
The invention aims to provide a composite-morphology nano-cellulose transparent film based on waste paper, which has high crystallinity, good thermal property and oxygen barrier property and wide application prospect in the fields of packaging and the like.
The second purpose of the invention is to provide a preparation method of the composite morphology nano cellulose transparent film based on waste paper.
The first technical proposal adopted by the invention is that based on the composite morphology nano cellulose transparent film of waste paper,
the composition comprises the following components in percentage by weight: 1.59 to 1.97 percent of waste paper, 31.86 to 39.29 percent of deionized water, 0 to 0.38 percent of deinking agent and 58.52 to 66.14 percent of concentrated sulfuric acid with the mass fraction of 98 percent, wherein the sum of the weight percentages of the components is 100 percent.
The second technical scheme adopted by the invention is that the preparation method of the composite morphology nano cellulose transparent film based on waste paper comprises the following steps:
step 2, preparing waste paper fiber, which comprises the following specific operation steps:
step 2.1, crushing waste paper, adding deionized water and a deinking agent for soaking to obtain waste paper liquid;
step 2.2, pouring the waste paper liquid obtained in the step 2.1 into a pulping machine for pulping, pouring the waste paper liquid into a standard inspection sieve after pulping, washing the waste paper liquid with water for multiple times, removing floating foam, and draining water to obtain waste paper pulp;
step 2.3, placing the waste paper pulp into a culture dish, and placing the culture dish into an electric heating forced air drying box for drying to obtain a waste paper cake;
2.4, breaking the dried waste paper cakes into pieces, and putting the pieces into a crusher to crush the pieces to obtain waste paper fibers;
step 3, preparing the waste paper-based nano cellulose, and specifically comprising the following operation steps:
step 3.1, diluting concentrated sulfuric acid with the mass fraction of 98% to sulfuric acid with the mass fraction of 59%;
step 3.2, weighing waste paper fibers, adding diluted sulfuric acid, stirring until the diluted sulfuric acid is dissolved, and stirring the waste paper fibers in a water bath condition to obtain acidified suspension A;
step 3.3, diluting the suspension A by 10 times, cooling and standing to obtain a suspension B;
step 3.4, carrying out suction filtration washing on the suspension B, and dialyzing to obtain a neutral nano cellulose suspension;
step 3.5, after ultrasonically dispersing the neutral nano-cellulose suspension, pouring the suspension into a culture dish, and carrying out freeze drying to obtain waste paper-based nano-cellulose;
step 4, preparing the waste paper-based nano cellulose transparent film, which comprises the following specific operation steps:
step 4.1, adding deionized water into the nano-cellulose prepared in the step 3.5 to prepare a nano-cellulose suspension, and ultrasonically dispersing the nano-cellulose suspension;
step 4.2, performing vacuum filtration on the nano-cellulose suspension by using a sand core filtering device to obtain a wet nano-cellulose film;
and 4.3, taking down the wet nano-cellulose film and the microporous filter membrane together, and drying the wet nano-cellulose film and the microporous filter membrane by using an air gun to obtain the waste paper-based composite morphology nano-cellulose transparent film finally.
The present invention is also characterized in that,
the deinking agent comprises the following components in percentage by mass: h2O2：NaOH：Na2SiO3：SDBS： OP-10＝2.8～3.2：0.4～0.5：1.3～1.6：0.35～0.45：0.45～0.55。
In the step 2.1, the waste paper is crushed into fragments with the size of 15mm multiplied by 4mm to 20mm multiplied by 10mm, and the soaking time in deionized water is 20min to 40 min; in the step 2.2, the pulping time of the waste paper liquid is 20 min-40 min, and the standard inspection sieve is 300 meshes-350 meshes.
In the step 2.3, the drying temperature of the waste paper pulp is 80-90 ℃, and the drying time is 20-24 h.
In the step 2.4, the crushing power of the waste paper cake is 1000 w-1400 w, the crushing times are 2 times, the single crushing time is 20 s-40 s, and the interval time is 10 s-15 s.
In the step 3.2, the temperature of the water bath is 40-50 ℃, the stirring speed is 250-290 r/min, and the stirring time is 1 h; the standing time in the step 3.3 is 1 h; in the step 3.4, the suction filtration time is 1-2 h, and the dialysis time is 3-4 d.
In the step 3.5, the ultrasonic time is 20 min-40 min, the freeze drying temperature is-65 ℃ to-55 ℃, and the freeze drying time is 2 d-3 d.
In the step 4.1, the ultrasonic time is 20 min-40 min.
In the step 4.2, the vacuum filtration time is 1.5 h-2.5 h, the material of the filter membrane is polyvinylidene fluoride, and the aperture of the filter membrane is 0.22 mu m; and in the step 4.3, the air gun drying time is 20-40 min.
The invention has the beneficial effects that:
in the nano-cellulose film prepared by the invention, on a microscopic level, the nano-cellulose film has a regular composite appearance, namely, the nano-fibers are arranged in an oriented manner in the middle of the film, and the edges of the nano-cellulose film are randomly arranged; nanocellulose has a high degree of crystallinity. Macroscopically, the nano-cellulose film has certain transparency and does not depend on the type of paper and whether deinking is carried out or not; in addition, the nano-cellulose film has good thermal stability and oxygen barrier property. In conclusion, the invention takes the waste paper as the raw material, adopts a simple preparation process and lower preparation cost to prepare the nano cellulose transparent film with the composite morphology, has higher crystallinity, good thermal property and oxygen barrier property, has wide application prospect in the fields of packaging and the like, realizes the recycling of the waste paper, obtains a new product with higher added value, and creates economic benefit and environmental benefit.
Drawings
FIG. 1 is a schematic diagram of a nano-cellulose film prepared in example 1 of the present invention;
FIG. 2 is a schematic diagram of a nano-cellulose film prepared in example 2 of the present invention;
FIG. 3 is a schematic diagram of a nano-cellulose film prepared in example 3 of the present invention;
FIG. 4 is a schematic diagram of a nano-cellulose film prepared in example 4 of the present invention;
FIG. 5 is a schematic view of a nano-cellulose film prepared in example 5 of the present invention;
FIG. 6 is a schematic view of a nano-cellulose film prepared in example 6 of the present invention;
FIG. 7 is a scanning electron microscope image of the center of the transparent film of nano-cellulose prepared in example 1 of the present invention;
FIG. 8 is a scanning electron microscope image of the edge of the transparent film of nano-cellulose prepared in example 1 of the present invention;
FIG. 9 is a scanning electron microscope image of the center of the transparent film of nano-cellulose prepared in example 2 of the present invention;
FIG. 10 is a scanning mirror image of the edge of the transparent film of nano-cellulose prepared in example 2 of the present invention;
FIG. 11 is a scanning mirror image of the center of a transparent film of nanocellulose prepared in example 3 of the present invention;
FIG. 12 is a scanning mirror image of the edge of the transparent film of nano-cellulose prepared in example 3 of the present invention.
FIG. 13 is a scanning mirror image of the center of a transparent film of nanocellulose prepared in example 4 of the present invention;
FIG. 14 is a scanning mirror image of the edge of the transparent film of nano-cellulose prepared in example 4 of the present invention;
FIG. 15 is a scanning mirror image of the center of a transparent film of nanocellulose prepared in example 5 of the present invention;
FIG. 16 is a scanning mirror image of the edge of the transparent film of nano-cellulose prepared in example 5 of the present invention;
FIG. 17 is a scanning mirror image of the center of a transparent film of nanocellulose prepared in example 6 of the present invention;
FIG. 18 is a scanning mirror image of the edge of the transparent film of nano-cellulose prepared in example 6 of the present invention.
FIG. 19 is a graph of the transmittance of the nano-cellulose films prepared in examples 1, 2 and 3 of the present invention, which shows that the prepared nano-cellulose films all have a certain transparency;
FIG. 20 is a TG plot of nanocellulose films prepared by examples 3, 4, 5 of the present invention;
FIG. 21 is a graph showing the oxygen permeability of the nanocellulose films produced in examples 1, 2 and 3 of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention provides a waste paper-based composite-morphology nano-cellulose transparent film, which comprises the following raw material components in percentage by weight: 1.59 to 1.97 percent of waste paper, 31.86 to 39.29 percent of deionized water, 0 to 0.38 percent of deinking agent and 58.52 to 66.14 percent of concentrated sulfuric acid with the mass fraction of 98 percent, wherein the sum of the weight percentages of the components is 100 percent.
The invention also provides a preparation method of the waste paper-based composite-morphology nano-cellulose transparent film, which comprises the following steps:
in the step 1, the deinking agent comprises the following components in percentage by mass: h2O2：NaOH：Na2SiO3：SDBS： OP-10＝2.8～3.2：0.4～0.5：1.3～1.6：0.35～0.45：0.45～0.55。
Step 2, preparing waste paper fiber, which comprises the following specific operation steps:
step 2.1, crushing the waste paper into fragments of 15mm multiplied by 4mm to 20mm multiplied by 10mm, adding deionized water and a deinking agent, and soaking for 20min to 40min to obtain waste paper liquid;
step 2.2, pouring the waste paper liquid obtained in the step 2.1 into a pulping machine for pulping for 20-40 min, pouring the waste paper liquid into a standard inspection sieve of 300-350 meshes after pulping is finished, washing the waste paper liquid with water for multiple times, removing floating foams, and draining water to obtain waste paper pulp;
step 2.3, placing the waste paper pulp into a culture dish, placing the culture dish into an electric heating forced air drying box, and drying the culture dish for 20 to 24 hours at the temperature of between 80 and 90 ℃ to obtain a waste paper cake;
2.4, breaking the dried waste paper cakes into pieces, putting the pieces into a crusher, crushing the pieces for 2 times at 1000-1400 w, 20-40 s each time at intervals of 10-15 s, and crushing the pieces to obtain waste paper fibers;
step 3, preparing the waste paper-based nano cellulose, and specifically comprising the following operation steps:
step 3.1, diluting 98% concentrated sulfuric acid to sulfuric acid with the mass fraction of 59% concentration;
step 3.2, adding the diluted sulfuric acid into the waste paper fiber obtained in the step 2, stirring until the waste paper fiber is dissolved, heating the waste paper fiber in a water bath, and stirring for 1 hour to obtain acidified suspension A; wherein the water bath temperature is 40-50 ℃, and the stirring speed is 250-290 r/min;
step 3.3, diluting the suspension A by 10 times, cooling and standing for 1h to obtain a suspension B;
step 3.4, carrying out suction filtration and washing on the suspension B for 1-2 h, and dialyzing for 3-4 d to obtain a neutral nano cellulose suspension;
step 3.5, ultrasonically dispersing the neutral nano-cellulose suspension for 20-40 min, pouring the suspension into a culture dish, and freeze-drying the suspension for 2-3 d at the temperature of-65-55 ℃ to obtain waste paper-based nano-cellulose;
step 4, preparing the waste paper-based nano cellulose transparent film, which comprises the following specific operation steps:
step 4.1, preparing the nano-cellulose prepared in the step 3.5 into nano-cellulose suspension, and ultrasonically dispersing the nano-cellulose suspension for 20-40 min;
step 4.2, performing vacuum filtration on the nano-cellulose suspension for 1.5-2.5 h by using a sand core filtering device and a polyvinylidene fluoride filtering membrane with the aperture of 0.22 mu m to obtain a wet nano-cellulose membrane;
and 4.3, taking down the wet nano-cellulose film and the microporous filter membrane together, and blowing for 20-40 min by using an air gun to separate the nano-cellulose film from the microporous filter membrane, thereby finally obtaining the waste paper-based composite-shape nano-cellulose transparent film.
Wherein: waste paper, collected waste a4 paper (no ink, with ink), waste corrugated paper (no ink, with ink), waste white cardboard (no ink, with ink); 98% sulfuric acid (H)2SO4) Analytically pure, Tianjin, Tianli chemical reagent, Inc.; deionized water, analytically pure, na baichuan water treatment facilities ltd, guan city; the deinking agent comprises the following components: hydrogen peroxide (H)2O2) Analytically pure, Fuyu Fine chemical Co., Ltd, Tianjin; sodium hydroxide (NaOH), analytical grade, tianjin limited naturaceutical agents; sodium silicate (Na)2SiO3) Analytically pure, Tianjin, Tianli chemical reagent, Inc.; sodium Dodecyl Benzene Sulfonate (SDBS), analytically pure, tianjin city, natro chemical reagents ltd; OP-10, analytical pure, Tianjin Yongcheng Fine chemical Co., Ltd.
Example 1
The preparation method of the composite-morphology nano-cellulose transparent film based on the waste paper comprises the following steps:
step 2, preparing waste paper fiber, which comprises the following specific operation steps:
step 2.1, crushing the waste paper into fragments of 20mm multiplied by 10mm, adding deionized water and soaking for 40min to obtain waste paper liquid;
step 2.2, pouring the waste paper liquid obtained in the step 2.1 into a pulping machine for pulping for 40min, pouring the waste paper liquid into a standard inspection sieve with 325 meshes after pulping is finished, washing the waste paper liquid with water for multiple times, removing floating foam, and draining water to obtain waste paper pulp;
step 2.3, placing the waste paper pulp into a culture dish, placing the culture dish into an electric heating forced air drying box, and drying the culture dish for 24 hours at the temperature of 80 ℃ to obtain a waste paper cake;
2.4, breaking the dried waste paper cake, putting the broken waste paper cake into a crusher, crushing the broken waste paper cake for 2 times at 1000w, 40s each time and 10s intervals, and crushing the broken waste paper cake to obtain waste paper fibers;
step 3, preparing the waste paper-based nano cellulose, and specifically comprising the following operation steps:
step 3.1, diluting 98% concentrated sulfuric acid to sulfuric acid with the mass fraction of 59% concentration;
step 3.2, adding the diluted sulfuric acid into the waste paper fiber obtained in the step 2, stirring until the waste paper fiber is dissolved, heating the waste paper fiber in a water bath, and stirring for 1 hour to obtain acidified suspension A; wherein the water bath temperature is 40 ℃, and the stirring speed is 290 r/min;
step 3.3, diluting the suspension A by 10 times, cooling and standing for 1h to obtain a suspension B;
step 3.4, carrying out suction filtration and washing on the suspension B for 2 hours, and dialyzing for 3 days to obtain a neutral nano cellulose suspension;
step 3.5, ultrasonically dispersing the neutral nano-cellulose suspension for 20min, pouring the suspension into a culture dish, and freeze-drying for 3d at the temperature of-60 ℃ to obtain waste paper-based nano-cellulose;
step 4, preparing the waste paper-based nano cellulose transparent film, which comprises the following specific operation steps:
step 4.1, preparing the nano-cellulose prepared in the step 3.5 into nano-cellulose suspension, and ultrasonically dispersing the nano-cellulose suspension for 20 min;
step 4.2, performing vacuum filtration on the nano-cellulose suspension for 2 hours by using a sand core filtering device and a polyvinylidene fluoride filtering membrane with the aperture of 0.22 mu m in the sand core filtering device to obtain a wet nano-cellulose film;
and 4.3, taking down the wet nano-cellulose film and the microporous filter membrane together, and blowing for 30min by using an air gun to separate the nano-cellulose film from the microporous filter membrane, thereby finally obtaining the waste paper-based composite morphology nano-cellulose transparent film.
As can be seen from fig. 1 and 19, the nanocellulose film has a certain transparency; as can be seen from fig. 7 and 8, the micro-morphologies of the middle portion and the edges of the nanocellulose film are different, the middle portion is arranged in a certain orientation, and the edges are randomly arranged, i.e., have a regular composite morphology; from FIG. 21, it can be seen that the oxygen transmission of the nanocellulose film was 1.54. multidot.10-3/cm3·mm/m2D KPa has higher oxygen barrier performance.
Example 2
A preparation method of a composite-morphology nano-cellulose transparent film based on waste paper comprises the following steps:
Step 2, preparing waste paper fiber, which comprises the following specific operation steps:
step 2.1, crushing the waste paper into pieces of 18mm multiplied by 8mm, adding deionized water and a deinking agent, and soaking for 30min to obtain waste paper liquid;
step 2.2, pouring the waste paper liquid obtained in the step 2.1 into a pulping machine for pulping for 30min, pouring the waste paper liquid into a standard inspection sieve with 325 meshes after the pulping is finished, washing the waste paper liquid with water for multiple times, removing floating foam, and draining water to obtain waste paper pulp;
step 2.3, placing the waste paper pulp into a culture dish, placing the culture dish into an electric heating forced air drying box, and drying the culture dish for 24 hours at the temperature of 80 ℃ to obtain a waste paper cake;
2.4, breaking the dried waste paper cake, putting the broken waste paper cake into a crusher, crushing the broken waste paper cake for 2 times at 1200w, 30s each time and 10s intervals, and crushing the broken waste paper cake to obtain waste paper fibers;
step 3, preparing the waste paper-based nano cellulose, and specifically comprising the following operation steps:
step 3.1, diluting 98% concentrated sulfuric acid to 59% concentration;
step 3.2, adding the diluted sulfuric acid into the waste paper fiber obtained in the step 2, stirring until the waste paper fiber is dissolved, heating the waste paper fiber in a water bath, and stirring for 1 hour to obtain acidified suspension A; wherein the water bath temperature is 45 ℃, and the stirring speed is 270 r/min;
step 3.3, diluting the suspension A by 10 times, cooling and standing for 1h to obtain a suspension B;
step 3.4, carrying out suction filtration and washing on the suspension B for 2 hours, and dialyzing for 3 days to obtain a neutral nano cellulose suspension;
step 3.5, ultrasonically dispersing the neutral nano-cellulose suspension for 30min, pouring the suspension into a culture dish, and freeze-drying for 3d at the temperature of-60 ℃ to obtain waste paper-based nano-cellulose;
step 4, preparing the waste paper-based nano cellulose transparent film, which comprises the following specific operation steps:
step 4.1, preparing the nano-cellulose prepared in the step 3.5 into nano-cellulose suspension, and ultrasonically dispersing the nano-cellulose suspension for 30 min;
step 4.2, performing vacuum filtration on the nano-cellulose suspension for 2 hours by using a sand core filtering device and a polyvinylidene fluoride filtering membrane with the aperture of 0.22 mu m to obtain a wet nano-cellulose film;
and 4.3, taking down the wet nano-cellulose film and the microporous filter membrane together, and blowing for 30min by using an air gun to separate the nano-cellulose film from the microporous filter membrane, thereby finally obtaining the waste paper-based composite morphology nano-cellulose transparent film.
As can be seen from fig. 2 and 19, the nanocellulose film has a certain transparency; as can be seen from fig. 9 and 10, the micro-morphologies of the middle portion and the edge of the nanocellulose film are different, the middle portion is arranged in a certain orientation, and the edge is randomly arranged, i.e., has a regular composite morphology; from FIG. 21, it can be seen that the oxygen transmission of the nanocellulose film was 5.608 · 10-3/cm3·mm/m2D KPa has higher oxygen barrier performance.
Example 3
A preparation method of a composite-morphology nano-cellulose transparent film based on waste paper comprises the following steps:
step 2, preparing waste paper fiber, which comprises the following specific operation steps:
step 2.1, crushing the waste paper into fragments of 15mm multiplied by 4mm, adding deionized water and soaking for 20min to obtain waste paper liquid;
step 2.2, pouring the waste paper liquid obtained in the step 2.1 into a pulping machine for pulping for 20min, pouring the waste paper liquid into a standard inspection sieve with 325 meshes after pulping is finished, washing the waste paper liquid with water for multiple times, removing floating foam, and draining water to obtain waste paper pulp;
step 2.3, placing the waste paper pulp into a culture dish, placing the culture dish into an electric heating forced air drying box, and drying the culture dish for 24 hours at the temperature of 80 ℃ to obtain a waste paper cake;
2.4, breaking the dried waste paper cake, putting the broken waste paper cake into a crusher, crushing the broken waste paper cake for 2 times at 1400w, 20s each time and 10s intervals, and crushing the broken waste paper cake to obtain waste paper fibers;
step 3, preparing the waste paper-based nano cellulose, and specifically comprising the following operation steps:
step 3.1, diluting 98% concentrated sulfuric acid to 59% concentration;
step 3.2, adding the diluted sulfuric acid into the waste paper fiber obtained in the step 2, stirring until the waste paper fiber is dissolved, heating the waste paper fiber in a water bath, and stirring for 1 hour to obtain acidified suspension A; wherein the water bath temperature is 50 ℃, and the stirring speed is 250 r/min;
step 3.3, diluting the suspension A by 10 times, cooling and standing for 1h to obtain a suspension B;
step 3.4, carrying out suction filtration and washing on the suspension B for 2 hours, and dialyzing 3 to obtain a neutral nano cellulose suspension;
step 3.5, ultrasonically dispersing the neutral nano-cellulose suspension for 40min, pouring the suspension into a culture dish, and freeze-drying for 3d at the temperature of-60 ℃ to obtain waste paper-based nano-cellulose;
step 4, preparing the waste paper-based nano cellulose transparent film, which comprises the following specific operation steps:
step 4.1, preparing the nano-cellulose prepared in the step 3.5 into nano-cellulose suspension, and ultrasonically dispersing the nano-cellulose suspension for 40 min;
step 4.2, performing vacuum filtration on the nano-cellulose suspension for 2 hours by using a sand core filtering device and a polyvinylidene fluoride filtering membrane with the aperture of 0.22 mu m to obtain a wet nano-cellulose film;
and 4.3, taking down the wet nano-cellulose film and the microporous filter membrane together, and blowing for 30min by using an air gun to separate the nano-cellulose film from the microporous filter membrane, thereby finally obtaining the waste paper-based composite morphology nano-cellulose transparent film.
From fig. 3 and 19, it can be seen that the nanocellulose film has a certain transparency; as can be seen from FIGS. 11 and 12, the micro-morphologies of the center and the edge of the nanocellulose film were different, with the center portion beingThe edges are randomly arranged, namely the edges have regular composite morphology; the calculation can obtain the nano cellulose with higher crystallinity which is 43 percent; as can be seen from fig. 20, the thermal stability of the nanocellulose film is good, and the nanocellulose starts to be thermally decomposed from 143 ℃; from FIG. 21, it can be seen that the oxygen transmission of the nanocellulose film was 40.448 · 10-3/cm3·mm/m2d.KPa, with higher oxygen barrier performance.
Example 4
A preparation method of a composite-morphology nano-cellulose transparent film based on waste paper comprises the following steps:
step 2, preparing waste paper fiber, which comprises the following specific operation steps:
step 2.1, crushing the waste paper into fragments of 20mm multiplied by 10mm, adding deionized water and soaking for 40min to obtain waste paper liquid;
step 2.2, pouring the waste paper liquid obtained in the step 2.1 into a pulping machine for pulping for 40min, pouring the waste paper liquid into a standard inspection sieve with 325 meshes after pulping is finished, washing the waste paper liquid with water for multiple times, removing floating foam, and draining water to obtain waste paper pulp;
step 2.3, placing the waste paper pulp into a culture dish, placing the culture dish into an electric heating forced air drying box, and drying the culture dish for 24 hours at the temperature of 80 ℃ to obtain a waste paper cake;
2.4, breaking the dried waste paper cake, putting the broken waste paper cake into a crusher, crushing the broken waste paper cake for 2 times at 1000w, 40s each time and 10s intervals, and crushing the broken waste paper cake to obtain waste paper fibers;
step 3, preparing the waste paper-based nano cellulose, and specifically comprising the following operation steps:
step 3.1, diluting 98% concentrated sulfuric acid to 59% concentration;
step 3.2, adding the diluted sulfuric acid into the waste paper fiber obtained in the step 2, stirring until the waste paper fiber is dissolved, heating the waste paper fiber in a water bath, and stirring for 1 hour to obtain acidified suspension A; wherein the water bath temperature is 40 ℃, and the stirring speed is 290 r/min;
step 3.3, diluting the suspension A by 10 times, cooling and standing for 1h to obtain a suspension B;
step 3.4, carrying out suction filtration and washing on the suspension B for 2 hours, and dialyzing for 3 days to obtain a neutral nano cellulose suspension;
step 3.5, ultrasonically dispersing the neutral nano-cellulose suspension for 20min, pouring the suspension into a culture dish, and freeze-drying for 3d at the temperature of-60 ℃ to obtain waste paper-based nano-cellulose;
step 4, preparing the waste paper-based nano cellulose transparent film, which comprises the following specific operation steps:
step 4.1, preparing the nano-cellulose prepared in the step 3.5 into nano-cellulose suspension, and ultrasonically dispersing the nano-cellulose suspension for 20 min;
step 4.2, performing vacuum filtration on the nano-cellulose suspension for 2 hours by using a sand core filtering device and a polyvinylidene fluoride filtering membrane with the aperture of 0.22 mu m to obtain a wet nano-cellulose film;
and 4.3, taking down the wet nano-cellulose film and the microporous filter membrane together, and blowing for 30min by using an air gun to separate the nano-cellulose film from the microporous filter membrane, thereby finally obtaining the waste paper-based composite morphology nano-cellulose transparent film. From fig. 4 and 19, it can be seen that the nanocellulose film has a certain transparency; as can be seen from fig. 13 and 14, the micro-morphologies of the middle portion and the edge of the nanocellulose film are different, the middle portion is arranged in a certain orientation, and the edge is randomly arranged, i.e., has a regular composite morphology; the calculation shows that the nano cellulose has higher crystallinity which is 35 percent; from fig. 20, it can be seen that the thermal stability of the nanocellulose film is better, and the nanocellulose starts to be thermally decomposed from 207 ℃.
Example 5
A preparation method of a composite-morphology nano-cellulose transparent film based on waste paper comprises the following steps:
step 2, preparing waste paper fiber, which comprises the following specific operation steps:
step 2.1, crushing the waste paper into fragments of 18mm multiplied by 8mm, adding deionized water and soaking for 30min to obtain waste paper liquid;
step 2.2, pouring the waste paper liquid obtained in the step 2.1 into a pulping machine for pulping for 30min, pouring the waste paper liquid into a standard inspection sieve with 325 meshes after the pulping is finished, washing the waste paper liquid with water for multiple times, removing floating foam, and draining water to obtain waste paper pulp;
step 2.3, placing the waste paper pulp into a culture dish, placing the culture dish into an electric heating forced air drying box, and drying the culture dish for 24 hours at the temperature of 80 ℃ to obtain a waste paper cake;
2.4, breaking the dried waste paper cake, putting the broken waste paper cake into a crusher, crushing the broken waste paper cake for 2 times at 1200w, 30s each time and 10s intervals, and crushing the broken waste paper cake to obtain waste paper fibers;
step 3, preparing the waste paper-based nano cellulose, and specifically comprising the following operation steps:
step 3.1, diluting 98% concentrated sulfuric acid to 59% concentration;
step 3.2, adding the diluted sulfuric acid into the waste paper fiber obtained in the step 2, stirring until the waste paper fiber is dissolved, heating the waste paper fiber in a water bath, and stirring for 1 hour to obtain acidified suspension A; wherein the water bath temperature is 45 ℃, and the stirring speed is 270 r/min;
step 3.3, diluting the suspension A by 10 times, cooling and standing for 1h to obtain a suspension B;
step 3.4, carrying out suction filtration and washing on the suspension B for 2 hours, and dialyzing for 3 days to obtain a neutral nano cellulose suspension;
step 3.5, ultrasonically dispersing the neutral nano-cellulose suspension for 30min, pouring the suspension into a culture dish, and freeze-drying for 3d at the temperature of-60 ℃ to obtain waste paper-based nano-cellulose;
step 4, preparing the waste paper-based nano cellulose transparent film, which comprises the following specific operation steps:
step 4.1, preparing the nano-cellulose prepared in the step 3.5 into nano-cellulose suspension, and ultrasonically dispersing the nano-cellulose suspension for 30 min;
step 4.2, performing vacuum filtration on the nano-cellulose suspension for 2 hours by using a sand core filtering device and a polyvinylidene fluoride filtering membrane with the aperture of 0.22 mu m to obtain a wet nano-cellulose film;
and 4.3, taking down the wet nano-cellulose film and the microporous filter membrane together, and blowing for 30min by using an air gun to separate the nano-cellulose film from the microporous filter membrane, thereby finally obtaining the waste paper-based composite morphology nano-cellulose transparent film.
As can be seen from fig. 5 and 19, the nanocellulose film has a certain transparency; as can be seen from fig. 15 and 16, the micro-morphologies of the middle portion and the edge of the nanocellulose film are different, the middle portion is arranged in a certain orientation, and the edge is randomly arranged, i.e., has a regular composite morphology; fig. 20 shows that the thermal stability of the nanocellulose film is better, and the nanocellulose starts to be thermally decomposed from 174 ℃.
Example 6
A preparation method of a composite-morphology nano-cellulose transparent film based on waste paper comprises the following steps:
Step 2, preparing waste paper fiber, which comprises the following specific operation steps:
step 2.1, crushing the waste paper into fragments of 15mm multiplied by 4mm, adding deionized water and a deinking agent, and soaking for 20min to obtain waste paper liquid;
step 2.2, pouring the waste paper liquid obtained in the step 2.1 into a pulping machine for pulping for 20min, pouring the waste paper liquid into a standard inspection sieve with 325 meshes after pulping is finished, washing the waste paper liquid with water for multiple times, removing floating foam, and draining water to obtain waste paper pulp;
step 2.3, placing the waste paper pulp into a culture dish, placing the culture dish into an electric heating forced air drying box, and drying the culture dish for 24 hours at the temperature of 80 ℃ to obtain a waste paper cake;
2.4, breaking the dried waste paper cake, putting the broken waste paper cake into a crusher, crushing the broken waste paper cake for 2 times at 1400w, 20s each time and 10s intervals, and crushing the broken waste paper cake to obtain waste paper fibers;
step 3, preparing the waste paper-based nano cellulose, and specifically comprising the following operation steps:
step 3.1, diluting 98% concentrated sulfuric acid to 59% concentration;
step 3.2, adding the diluted sulfuric acid into the waste paper fiber obtained in the step 2, stirring until the waste paper fiber is dissolved, heating the waste paper fiber in a water bath, and stirring for 1 hour to obtain acidified suspension A; wherein the water bath temperature is 50 ℃, and the stirring speed is 250 r/min;
step 3.3, diluting the suspension A by 10 times, cooling and standing for 1h to obtain a suspension B;
step 3.4, carrying out suction filtration and washing on the suspension B for 2 hours, and dialyzing for 3 days to obtain a neutral nano cellulose suspension;
step 3.5, ultrasonically dispersing the neutral nano-cellulose suspension for 40min, pouring the suspension into a culture dish, and freeze-drying for 3d at the temperature of-60 ℃ to obtain waste paper-based nano-cellulose;
step 4, preparing the waste paper-based nano cellulose transparent film, which comprises the following specific operation steps:
step 4.1, preparing the nano-cellulose prepared in the step 3.5 into nano-cellulose suspension, and ultrasonically dispersing the nano-cellulose suspension for 40 min;
step 4.2, performing vacuum filtration on the nano-cellulose suspension for 2 hours by using a sand core filtering device and a polyvinylidene fluoride filtering membrane with the aperture of 0.22 mu m to obtain a wet nano-cellulose film;
and 4.3, taking down the wet nano-cellulose film and the microporous filter membrane together, and blowing for 30min by using an air gun to separate the nano-cellulose film from the microporous filter membrane, thereby finally obtaining the waste paper-based composite morphology nano-cellulose transparent film. As can be seen from fig. 6 and 19, the nanocellulose film has a certain transparency; as can be seen from fig. 17 and 18, the micro-morphologies of the middle portion and the edge of the nanocellulose film are different, the middle portion is arranged in a certain orientation, and the edge is randomly arranged, i.e., has a regular composite morphology; the calculation shows that the nano-cellulose has higher crystallinity which is 61%.
It is observed that the transparent film of nano-cellulose can be prepared in the examples 1 to 6. In order to further understand the morphology structure of the film, microscopic observation is carried out on the films prepared in the embodiments 1 to 6 by using a field emission scanning electron microscope, and the obtained celluloses are all in a short rod-shaped structure, the diameter is 20nm to 50nm, the length is 100nm to 400nm, the cellulose fibers are all in a nanometer grade, the orientation of the nanocellulose in the middle part of the film is strong, and the edge parts of the nanocellulose are randomly arranged; the crystallinity of the nano-cellulose film is calculated, so that the nano-cellulose with higher crystallinity can be obtained, wherein the crystallinity of the nano-cellulose prepared from the waste corrugated paper can reach 61%; thermogravimetric analysis is carried out on the nano cellulose film, and the thermal stability of the nano cellulose film is better according to a TG picture, wherein the thermal decomposition temperature of the nano cellulose prepared by the waste white cardboard is as high as 207 ℃; oxygen transmission rate detection is carried out on the nano-cellulose film, and according to an oxygen transmission rate graph, the nano-cellulose film has high oxygen barrier performance, wherein the minimum oxygen transmission rate of the nano-cellulose film prepared from the waste A4 paper is 1.548-10-3/cm3·mm/m2·d·KPa。
The nano cellulose film based on waste paper prepared by the invention has the following characteristics: microscopically, the nano cellulose film has regular composite appearance, namely, the nano fibers are arranged in an oriented way in the middle of the film, and the edges of the nano fibers are randomly arranged; nanocellulose has a high degree of crystallinity. Macroscopically, the nano cellulose film has certain transparency and does not depend on the type of paper and whether deinking is carried out or not, so that the process flow can be simplified, and the production cost can be reduced; in addition, the nano cellulose film has good thermal stability and oxygen barrier property, and has wide application prospect in the fields of packaging and the like. In conclusion, the invention provides the preparation method of the nano-cellulose transparent film based on the composite morphology of the waste paper, which not only realizes the recycling of the waste paper, but also obtains products with higher added value through a simple preparation process and lower preparation cost, and creates economic benefits and environmental benefits.
Claims (10)
1. The composite morphology nano-cellulose transparent film based on waste paper is characterized by comprising the following components in percentage by weight: 1.59 to 1.97 percent of waste paper, 31.86 to 39.29 percent of deionized water, 0 to 0.38 percent of deinking agent and 58.52 to 66.14 percent of concentrated sulfuric acid with the mass fraction of 98 percent, wherein the sum of the weight percentages of the components is 100 percent.
2. The preparation method of the composite-morphology nano-cellulose transparent film based on waste paper is characterized by comprising the following steps:
step 1, weighing the following components in parts by weight: 1.59 to 1.97 percent of waste paper, 31.86 to 39.29 percent of deionized water, 0 to 0.38 percent of deinking agent and 58.52 to 66.14 percent of concentrated sulfuric acid with the mass fraction of 98 percent, wherein the sum of the weight percentages of the components is 100 percent;
step 2, preparing waste paper fiber, which comprises the following specific operation steps:
step 2.1, crushing waste paper, adding deionized water and a deinking agent for soaking to obtain waste paper liquid;
step 2.2, pouring the waste paper liquid obtained in the step 2.1 into a pulping machine for pulping, pouring the waste paper liquid into a standard inspection sieve after pulping, washing the waste paper liquid with water for multiple times, removing floating foam, and draining water to obtain waste paper pulp;
step 2.3, placing the waste paper pulp into a culture dish, and placing the culture dish into an electric heating forced air drying box for drying to obtain a waste paper cake;
2.4, breaking the dried waste paper cakes into pieces, and putting the pieces into a crusher to crush the pieces to obtain waste paper fibers;
step 3, preparing the waste paper-based nano cellulose, and specifically comprising the following operation steps:
step 3.1, diluting concentrated sulfuric acid with the mass fraction of 98% to sulfuric acid with the mass fraction of 59%;
step 3.2, weighing waste paper fibers, adding diluted sulfuric acid, stirring until the diluted sulfuric acid is dissolved, and stirring the waste paper fibers in a water bath condition to obtain acidified suspension A;
step 3.3, diluting the suspension A by 10 times, cooling and standing to obtain a suspension B;
step 3.4, carrying out suction filtration washing on the suspension B, and dialyzing to obtain a neutral nano cellulose suspension;
step 3.5, after ultrasonically dispersing the neutral nano-cellulose suspension, pouring the suspension into a culture dish, and carrying out freeze drying to obtain waste paper-based nano-cellulose;
step 4, preparing the waste paper-based nano cellulose transparent film, which comprises the following specific operation steps:
step 4.1, adding deionized water into the nano-cellulose prepared in the step 3.5 to prepare a nano-cellulose suspension, and ultrasonically dispersing the nano-cellulose suspension;
step 4.2, performing vacuum filtration on the nano-cellulose suspension by using a sand core filtering device to obtain a wet nano-cellulose film;
and 4.3, taking down the wet nano-cellulose film and the microporous filter membrane together, and drying the wet nano-cellulose film and the microporous filter membrane by using an air gun to obtain the waste paper-based composite morphology nano-cellulose transparent film finally.
3. The preparation method of the waste paper-based composite-morphology nanocellulose transparent film according to claim 2, characterized in that the deinking agent in step 1 comprises the following components in percentage by mass: h2O2：NaOH：Na2SiO3：SDBS：OP-10＝2.8～3.2：0.4～0.5：1.3～1.6：0.35～0.45：0.45～0.55。
4. The method for preparing the waste paper-based composite morphology nano cellulose transparent film according to claim 2, characterized in that the waste paper in the step 2.1 is crushed into fragments of 15mm x 4mm to 20mm x 10mm, and the soaking time in the deionized water is 20min to 40 min; in the step 2.2, the pulping time of the waste paper liquid is 20 min-40 min, and the standard inspection sieve is 300 meshes-350 meshes.
5. The preparation method of the waste paper-based composite morphology nano-cellulose transparent film according to claim 2, characterized in that the drying temperature of the waste paper pulp in the step 2.3 is 80-90 ℃, and the drying time is 20-24 h.
6. The method for preparing the waste paper-based composite morphology nano-cellulose transparent film according to claim 2, characterized in that in the step 2.4, the crushing power of the waste paper cake is 1000 w-1400 w, the crushing times are 2 times, the single crushing time is 20 s-40 s, and the interval time is 10 s-15 s.
7. The preparation method of the waste paper-based composite morphology nano-cellulose transparent film according to claim 2, characterized in that the water bath temperature in the step 3.2 is 40-50 ℃, the stirring speed is 250-290 r/min, and the stirring time is 1 h; the standing time in the step 3.3 is 1 h; in the step 3.4, the suction filtration time is 1-2 h, and the dialysis time is 3-4 d.
8. The preparation method of the waste paper-based composite morphology nano-cellulose transparent film according to claim 2, characterized in that in the step 3.5, the ultrasonic time is 20 min-40 min, the freeze-drying temperature is-65 ℃ to-55 ℃, and the freeze-drying time is 2 d-3 d.
9. The preparation method of the waste paper-based composite morphology nano-cellulose transparent film according to claim 2, characterized in that the ultrasonic time in the step 4.1 is 20 min-40 min.
10. The preparation method of the waste paper-based composite morphology nano-cellulose transparent film according to claim 2, characterized in that the vacuum filtration time in the step 4.2 is 1.5 h-2.5 h, the material of the filter membrane is polyvinylidene fluoride, and the aperture of the filter membrane is 0.22 μm; and in the step 4.3, the air gun drying time is 20-40 min.
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