CN110615849B - Method for preparing microfibrillated cellulose by alkaline oxidation of chlorine dioxide or sodium chlorite - Google Patents
Method for preparing microfibrillated cellulose by alkaline oxidation of chlorine dioxide or sodium chlorite Download PDFInfo
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- CN110615849B CN110615849B CN201910926758.0A CN201910926758A CN110615849B CN 110615849 B CN110615849 B CN 110615849B CN 201910926758 A CN201910926758 A CN 201910926758A CN 110615849 B CN110615849 B CN 110615849B
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- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
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Abstract
The invention provides a method for preparing microfibrillated cellulose by alkaline oxidation of chlorine dioxide or sodium chlorite, which comprises the steps of mixing chemical pulp subjected to high-temperature self-hydrolysis treatment with a liquid medicine, adding the mixture into a reactor for alkaline oxidation, and then sequentially washing, grinding and homogenizing the pulp under high pressure until the microfibrillated cellulose is colloidal and has a size meeting the requirements. The preparation method adopts chlorine dioxide or sodium chlorite to oxidize paper pulp under alkaline conditions, ensures the stability of microfibrillated cellulose colloid, reduces the polymerization degree of cellulose, and is beneficial to the microfibrillation of the fiber during further mechanical treatment (high-pressure homogenization). The invention is characterized in that: firstly, the chemicals are simple and only need chlorine dioxide (or sodium chlorite) and sodium hydroxide; ② the yield is high; the microfibrillated cellulose colloid prepared by the method has good stability.
Description
Technical Field
The invention relates to the field of nano-cellulose preparation, in particular to a method for preparing microfibrillated cellulose by alkaline oxidation of chlorine dioxide or sodium chlorite.
Background
The cellulose is derived from trees, cotton, hemp and other agricultural and sideline products, is the most abundant natural high molecular substance in nature, and is taken from inexhaustible natural renewable resources which are the most valuable for human beings.
The nano-cellulose and the microfibrillated cellulose are high-strength light nano-materials and are new-generation green functional materials. The nano-composite material has the advantages of large specific surface area, high mechanical property, good biocompatibility, high composite activity, high transparency, low thermal expansion rate and the like, is a colloidal solution with extremely high swelling degree, and has the double characteristics of a nano material and a natural organic high polymer material. Has potential application value in the fields of paper making, food, cosmetics, composite materials and biomedicine. The research on microfibrillated cellulose (MFC) is gradually increased in China, and the preparation method, surface modification, characteristics, application thereof and the like of microfibrillated cellulose become research hotspots.
The methods for producing microfibrillated cellulose (MFC) mainly include chemical methods, mechanical methods, chemimechanical methods, biological methods, and the like. When MFC is produced chemically, it is generally produced by acid treatment, alkali treatment, TEMPO (2,2,6, 6-tetramethylpiperidinyloxy free radical) catalytic oxidation pretreatment, carboxymethylation treatment, and the like. Acid treatment not only results in a decrease in the strength of the cellulose but also results in a loss of its molecular mass; although the alkali treatment degrades the cellulose and affects the yield, it has an advantage of promoting the absorption of water; the TEMPO oxidation reaction can shorten the preparation time of the nano-cellulose, and can selectively oxidize primary alcohol hydroxyl of the cellulose and convert the primary alcohol hydroxyl into carboxyl. Baidu Baike, TEMPO (2,2,6, 6-tetramethylpiperidinyloxy radical) is toxic, corrosive, absorbed through the skin and strongly irritating. Therefore, it is very interesting to find a new oxidizing agent.
Disclosure of Invention
The invention aims to utilize the characteristic that chlorine dioxide reacts with carbohydrate (cellulose and hemicellulose) under different pH conditions, and oxidize paper pulp by using chlorine dioxide or sodium chlorite under alkaline conditions, on one hand, the carboxyl content of the cellulose is increased, the electronegativity of the cellulose is increased, and the Zeta potential of the pulp is reduced, so that the stability of microfibrillated cellulose colloid is ensured; on the other hand, the polymerization degree of the pulp (cellulose) is reduced, and the microfibrillation of the fiber during further mechanical treatment is facilitated. The main object of the present invention is to overcome the above-mentioned drawbacks and deficiencies of the prior art and to provide a process for the preparation of microfibrillated cellulose.
The preparation method of the microfibrillated cellulose comprises the following steps:
1. a method for preparing microfibrillated cellulose by alkaline oxidation of chlorine dioxide or sodium chlorite is characterized in that: the method for preparing microfibrillated cellulose by alkaline oxidation of chlorine dioxide (or sodium chlorite) of chemical pulp subjected to high-temperature self-hydrolysis treatment comprises the steps of alkaline oxidation of chlorine dioxide (or sodium chlorite) of high-temperature self-hydrolysis pulp-high-pressure homogenization, and specifically comprises the following steps in sequence:
(1) and (3) slurry scattering: adding water into the chemical pulp subjected to high-temperature self-hydrolysis treatment until the pulp concentration is 1-2%, and then scattering the pulp by using a scattering device;
(2) and (3) dehydrating: filtering and dehydrating the slurry obtained in the step (1) to obtain pretreated slurry;
(3) alkaline oxidation of chlorine dioxide (or sodium chlorite): mixing the pretreated slurry obtained in the step (2) with a liquid medicine (chlorine dioxide or sodium chlorite, sodium hydroxide and water), adding the mixture into a reaction vessel, adjusting the concentration of the slurry to be 5-20%, uniformly stirring, then reacting for 3-6 h at 60-95 ℃, wherein the initial reaction pH value is 8-11, the percentage of the mass of chlorine dioxide to the mass of the oven dry slurry is 3-12.0%, or the percentage of the mass of sodium chlorite to the mass of the oven dry slurry is 5-15%;
(4) washing the slurry: washing the slurry obtained in the step (3) with water to obtain oxidized slurry;
(5) grinding and decomposing: pulping the oxidized pulp obtained in the step (4) by using a pulping machine, and grinding fibers;
(6) high-pressure homogenization: homogenizing the slurry obtained in the step (5) for 10-90 times under the pressure of 20-90 MPa until the slurry is colloidal and the size meets the requirements of microfibrillated cellulose.
It should be noted that, the chemical pulp in the step (1) is softwood chemical pulp, hardwood chemical pulp or non-wood chemical pulp.
Further, the raw material of the non-wood chemical pulp in the step (1) comprises bamboo, cotton and hemp or grass plants.
The microfibrillated cellulose is obtained by carrying out alkaline oxidation on chemical pulp subjected to high-temperature self-hydrolysis treatment by chlorine dioxide or sodium chlorite and then homogenizing at high pressure, wherein the diameter of microfibrils of the microfibrillated cellulose is 20-120 nm, and the length-diameter ratio is more than 100.
2. Compared with the prior TEMPO oxidation method, the method has the characteristics that:
(1) the chemicals are simple, only chlorine dioxide (or sodium chlorite) and sodium hydroxide are needed;
(2) the yield is high.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to specific examples. While exemplary embodiments of the present disclosure are shown in the specific embodiments, it should be understood that the present disclosure may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
The present invention will be described in further detail with reference to specific examples.
Example 1
In this embodiment 1, a bleached softwood kraft pulp sheet is subjected to alkaline oxidation to prepare microfibrillated cellulose by using a mixed liquor of chlorine dioxide and sodium hydroxide as a research object, and the specific steps are as follows:
(1) and (3) slurry scattering: adding water into bleached softwood kraft pulp subjected to high-temperature self-hydrolysis treatment until the pulp concentration is 1-2%, and then scattering the bleached softwood kraft pulp by using a scattering device;
(2) and (3) dehydrating: filtering and dehydrating the slurry obtained in the step (1);
(3) alkaline oxidation of chlorine dioxide: mixing the slurry obtained in the step (2) with a liquid medicine (chlorine dioxide and sodium hydroxide), adding the mixture into a reaction vessel, adjusting the concentration of the slurry to 10%, uniformly stirring, reacting for 6 hours at 95 ℃, wherein the initial pH value of the reaction is 9.3, and the percentage of the mass of chlorine dioxide to the mass of oven-dry slurry is 9.5%;
(4) washing the slurry: washing the slurry obtained in the step (3) with water;
(5) grinding and decomposing: pulping the pulp obtained in the step (4) by using a pulping machine, and grinding fibers;
(6) high-pressure homogenization: homogenizing the slurry obtained in the step (5) for 35 times under the pressure of 80MPa to obtain the colloidal microfibrillated cellulose.
The microfibrillated cellulose prepared by the preparation method in example 1 has a diameter of microfibril of 20-100 nm and an aspect ratio of more than 100.
Example 2
In this embodiment, the method for preparing microfibrillated cellulose by alkaline oxidation of sodium chlorite and sodium hydroxide solution, which comprises the following steps:
(1) and (3) slurry scattering: adding water into the natural color softwood sulfite pulp subjected to high-temperature self-hydrolysis treatment until the pulp concentration is 1-2%, and then scattering the pulp by using a scattering device;
(2) and (3) dehydrating: filtering and dehydrating the slurry obtained in the step (1);
(3) alkaline oxidation of sodium chlorite: mixing the slurry obtained in the step (2) with a liquid medicine (sodium chlorite and sodium hydroxide) for oxidation, adding the mixture into a reaction container, adjusting the concentration of the slurry to be 10%, uniformly stirring the mixture, reacting the mixture for 5 hours at 95 ℃, wherein the initial pH value of the reaction is 10, and the mass percentage of the sodium chlorite to the mass of the oven-dry slurry is 15%;
(4) washing the slurry: washing the slurry obtained in the step (3) with water;
(5) grinding and decomposing: pulping the pulp obtained in the step (4) by using a pulping machine, and grinding fibers;
(6) high-pressure homogenization: homogenizing the slurry obtained in the step (5) for 20 times under the pressure of 80MPa to obtain the colloidal microfibrillated cellulose, wherein the diameter of microfibril is 20-120 nm, and the length-diameter ratio is more than 100.
The microfibrillated cellulose prepared by the preparation method in example 2 has a diameter of microfibril of 20-120 nm and an aspect ratio of more than 100.
Example 3
In this embodiment 3, a self-made sulfite pulp of eucalyptus globulus blue is used as a research object, and sodium chlorite liquid is used for alkaline oxidation to prepare microfibrillated cellulose, which includes the following steps:
(1) and (3) slurry scattering: adding water into self-made sulfite pulp of the eucalyptus globulus blue until the pulp concentration is 1% -2%, and then scattering the pulp by a scattering device;
(2) and (3) dehydrating: filtering and dehydrating the slurry obtained in the step (1);
(3) alkaline oxidation of sodium chlorite: mixing the slurry obtained in the step (2) with a liquid medicine (sodium chlorite and sodium hydroxide), adding the mixture into a reaction container, adjusting the concentration of the slurry to be 10%, uniformly stirring the mixture, reacting the mixture for 3 hours at 95 ℃, wherein the initial pH value of the reaction is 9, and the percentage of the mass of the sodium chlorite to the mass of the oven-dry slurry is 15%;
(4) washing the slurry: washing the slurry obtained in the step (3) with water;
(5) grinding and decomposing: pulping the pulp obtained in the step (4) by using a pulping machine, and grinding fibers;
(6) high-pressure homogenization: homogenizing the slurry obtained in the step (5) for 30 times under the pressure of 60MPa to obtain the colloidal microfibrillated cellulose.
The microfibrillated cellulose prepared by the preparation method in example 3 has a diameter of microfibril of 20-60 nm and an aspect ratio of more than 100.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (4)
1. A method for preparing microfibrillated cellulose by alkaline oxidation of chlorine dioxide or sodium chlorite is characterized in that: the method for preparing microfibrillated cellulose by chlorine dioxide or sodium chlorite alkaline oxidation of chemical pulp subjected to high-temperature self-hydrolysis comprises the steps of chlorine dioxide or sodium chlorite alkaline oxidation and high-pressure homogenization of the pulp, and specifically comprises the following steps in sequence:
(1) and (3) slurry scattering: adding water into the chemical pulp subjected to high-temperature self-hydrolysis treatment until the pulp concentration is 1-2%, and then scattering the pulp by using a scattering device;
(2) and (3) dehydrating: filtering and dehydrating the slurry obtained in the step (1) to obtain pretreated slurry;
(3) alkaline oxidation of chlorine dioxide or sodium chlorite: mixing the pretreated slurry obtained in the step (2) with a liquid medicine, adding the mixture into a reactor, adjusting the concentration of the slurry to be 5-20%, uniformly stirring, then reacting for 3-6 h at 60-95 ℃, wherein the initial pH value of the reaction is 8-11, the mass percentage of chlorine dioxide to the mass of the oven-dry slurry is 3-12.0%, or the mass percentage of sodium chlorite to the mass of the oven-dry slurry is 5-15%; the liquid medicine is chlorine dioxide or mixed liquid of sodium chlorite, sodium hydroxide and water;
(4) washing the slurry: washing the slurry obtained in the step (3) with water to obtain oxidized slurry;
(5) grinding and decomposing: pulping the oxidized pulp obtained in the step (4) by using a pulping machine, and grinding fibers;
(6) high-pressure homogenization: homogenizing the slurry obtained in the step (5) for 10-90 times under the pressure of 20-90 MPa until the microfibrillated cellulose which is colloidal and has the size meeting the requirement is obtained.
2. The method for preparing microfibrillated cellulose by alkaline oxidation of chlorine dioxide or sodium chlorite according to claim 1, wherein said chemical pulp in step 1 is softwood chemical pulp, hardwood chemical pulp or non-wood chemical pulp.
3. The method of claim 2, wherein the non-wood chemical pulp comprises bamboo, cotton, hemp or grass.
4. Microfibrillated cellulose prepared by the method for preparing microfibrillated cellulose by alkaline oxidation of chlorine dioxide or sodium chlorite according to any one of claims 1 to 3, wherein the microfibrillated cellulose has a microfibrillar diameter of 20 to 120nm and an aspect ratio of more than 100.
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| CN111471113A (en) * | 2020-06-16 | 2020-07-31 | 天津科技大学 | Preparation method of Cellulose Nanofibrils (CNF) |
| CN111979763A (en) * | 2020-09-16 | 2020-11-24 | 天津科技大学 | Method for preparing cellulose nanofibril CNF by treating polybasic acid |
Citations (4)
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| WO2007091942A1 (en) * | 2006-02-08 | 2007-08-16 | Stfi-Packforsk Ab | Method for the manufacturing of microfibrillated cellulose |
| EP2196579A1 (en) * | 2008-12-09 | 2010-06-16 | Borregaard Industries Limited, Norge | Method for producing microfibrillated cellulose |
| CN104831572A (en) * | 2015-02-13 | 2015-08-12 | 国际竹藤中心 | Method of preparing microfibrillated cellulose from bamboo parenchyma cells |
| CN104562823B (en) * | 2014-12-11 | 2017-01-18 | 天津科技大学 | Synchronization method for preparing microfibrillated cellulose and application of microfibrillated cellulose in strengthening of paper |
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Patent Citations (4)
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| WO2007091942A1 (en) * | 2006-02-08 | 2007-08-16 | Stfi-Packforsk Ab | Method for the manufacturing of microfibrillated cellulose |
| EP2196579A1 (en) * | 2008-12-09 | 2010-06-16 | Borregaard Industries Limited, Norge | Method for producing microfibrillated cellulose |
| CN104562823B (en) * | 2014-12-11 | 2017-01-18 | 天津科技大学 | Synchronization method for preparing microfibrillated cellulose and application of microfibrillated cellulose in strengthening of paper |
| CN104831572A (en) * | 2015-02-13 | 2015-08-12 | 国际竹藤中心 | Method of preparing microfibrillated cellulose from bamboo parenchyma cells |
Non-Patent Citations (2)
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