CN107602709B - Clean preparation method of carboxymethyl nano-cellulose material - Google Patents
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Abstract
The invention relates to a clean preparation method of a carboxymethyl nano-cellulose material. The carboxymethyl nano-cellulose material is obtained by pretreating cellulose raw materials, bleaching and oxygen pulping, continuous oxygen bleaching, crushing and activating pulp, etherifying, neutralizing, purifying and nanocrystallizing. The invention prepares cellulose pulp by cleanly pulping by taking various straws and plant waste residues as raw materials, then prepares the carboxymethyl cellulose nano-fiber, expands the range of the raw materials for preparing the nano-cellulose, has simple and coherent process, is environment-friendly and low in cost, opens up a new way for preparing the nano-cellulose, and provides wide prospect for the application of the nano-cellulose. The method provided by the invention can be used for directly preparing the functional nano cellulose fiber by using cellulose as a raw material, the prepared modified nano cellulose contains carboxyl and has good crystallinity, and the prepared nano cellulose has small crystal grains, thereby providing a good foundation for later application of products.
Description
Technical Field
The invention belongs to the field of fine chemical engineering, and particularly relates to a clean preparation method of a carboxymethyl nano-cellulose material.
Background
The nano-cellulose material is a cellulose product with the size of nano-scale obtained by performing acidolysis, enzymolysis, alkalization catalysis or mechanical shearing on cellulose of cotton, wood, straw and other types. In the prior art, according to different preparation methods, nano-Cellulose materials are mainly divided into two major classes of nano-Cellulose Crystals (CNWs) and nano-Cellulose Crystals (CNFs), and have performance advantages in different application occasions. The manufacturing method of the nano-cellulose material reported at home and abroad mainly comprises the following steps: chemical methods, physical methods, biological methods, synthetic methods, and the like. The biological enzymolysis method is time-consuming, high in cost and difficult, so that the preparation mode of the foreign cellulose nano material is mainly focused on a physical method and a chemical method at present. Chemical methods usually use strong acids for treatment, such as hydrochloric acid, sulfuric acid or phosphoric acid, and the acids are difficult to recover and high in cost after cellulose is hydrolyzed, and can only be used in laboratories at present; physical methods such as direct adoption of ultrasound, homogenization, mechanical crushing and ball milling and the like have great difficulty in achieving the nanoscale of cellulose, so that the nanoscale of a product is difficult to control, and meanwhile, the problems of high energy consumption and the like caused by strong treatment exist, so that the method does not enter an application stage.
In addition, if the cellulose is nanocrystallized and then carboxymethylated or esterified, the etherification of the nanocellulose is realized due to the defects of easy agglomeration, difficult dispersion, difficult control of a derivatization process, difficult collection and the like of the nanocellulose in alkali and an organic solvent, particularly the preparation difficulty of a mixed derivative material of the cellulose ether ester is higher, the nano characteristics of the nanocellulose are greatly damaged by alkalization, and if the etherification is realized through a chemical reaction, the continuous maintenance of the nano morphology of the cellulose is more difficult, so the nanocellulose with functional groups is difficult to directly prepare.
At present, plant cellulose products such as wheat, corn, cotton straw, bamboo, reed, straw residue and the like have rich sources and extremely strong regeneration capability, but at present, paper making and low-end weaving are still main utilization ways, and even the products are still treated by environmental pollution means such as incineration and the like, so that serious environmental pollution and waste of cellulose raw materials are brought, and therefore, the reasonable utilization of the products is the development direction of the fiber raw materials.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the rapid and clean preparation modified nano-cellulose and the preparation method thereof, wherein the rapid and clean preparation modified nano-cellulose has the advantages of rapidness, low cost, strong reaction controllability, high nano-cellulose whisker yield, simpler requirement on the pretreatment degree of raw materials, and capability of simultaneously preparing nano-whiskers and nano-fibers containing a small amount of ester groups and carboxyl groups.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a clean preparation method of a carboxymethyl nano-cellulose material, which comprises the following steps:
A. pretreatment of raw materials: adding a cellulose raw material into a pre-immersion liquid for pre-immersion and crushing, and bleaching by using a chlorine-free hydrogen peroxide system to remove a chromophore in the raw material;
B. the bleaching oxygen pulping technology comprises the following steps: concentrating the presoaked slurry, conveying the concentrated slurry to a mixer for mixing, and simultaneously adding bleaching liquor I to bleach the materials; the materials are preferably mixed using a high consistency mixer;
C. the continuous oxygen bleaching technology comprises the following steps: the pulp and the bleaching liquor II are conveyed to a continuous oxygen bleaching machine together by the mixer for bleaching again;
D. crushing and activating the slurry: crushing the pulp by a crusher, and swelling cellulose by an organic solvent and an alkali metal compound;
E. etherification: adding a mixture of an etherifying agent and an organic solvent, and etherifying at the temperature of 50-80 ℃;
F. neutralization and purification: neutralizing the base in the system with an acid; centrifuging the product, washing with water, and centrifuging again; deionized water is preferably used here;
G. nano-crystallization: and (3) diluting the centrifugal material with water, and then introducing the diluted centrifugal material into a high-pressure homogenizer for homogenization treatment to obtain carboxymethyl cellulose nanofibers, namely CMNFs.
Further, in the clean preparation method of the carboxymethyl nano-cellulose material, the pre-immersion liquid in the step A comprises the following components in percentage by weight: 2% of alkali, 0.4-0.5% of magnesium sulfate, 2-3% of layer silicon, 0.1% of sodium citrate, 0.3-0.5% of methylene phosphonic acid, 0.1% of penetrating agent and the balance of water. The alkali can be alkaline materials such as sodium hydroxide, potassium hydroxide and the like, the layered silicon is layered crystal sodium disilicate, and the penetrating agent is fatty alcohol-polyoxyethylene ether.
Further, in the clean preparation method of the carboxymethyl nano-cellulose material, the cellulose raw material in the step A is one or more of wheat straw, corn straw, rice straw, cotton straw, bamboo pulp, reed and bagasse, and the crushing granularity of the cellulose raw material is not more than 60 meshes.
Further, in the clean preparation method of the carboxymethyl nano-cellulose material, the presoaking temperature in the step A is 40-50 ℃, and the presoaking time is 40-60 min.
Further, in the above clean preparation method of carboxymethyl nanocellulose material, the bleaching liquor I in the step B is composed of the following components: hydrogen peroxide, alkali and Na2SiO3、MgSO4And NaBH4And (4) forming. Hydrogen peroxide i.e. H2O2The alkali may be inorganic alkali such as sodium hydroxide and potassium hydroxide.
Further, in the clean preparation method of the carboxymethyl nano-cellulose material, the bleaching liquor I in the step B comprises the following components in percentage by mass: 2-5% of hydrogen peroxide, 3-5% of alkali and 2% of Na2SiO3、MgSO4And NaBH4The bleaching agent and the balance of water.
Further, in the clean preparation method of the carboxymethyl nano-cellulose material, the bleaching liquor II in the step C consists of the following components in parts by weight: 300 parts of 27.5% hydrogen peroxide, 1 part of dicyandiamide catalyst, 60 parts of oxygen and 1 part of phenanthroline.
Further, in the clean preparation method of the carboxymethyl nano-cellulose material, the etherifying agent in the step E is an organic solvent of chloroacetic acid with the mass fraction of 40-60%, and the etherification time is 1-4 hours; and D, the mass ratio of the cellulose pulp obtained in the step D to the chloroacetic acid is 1: (0.20-0.50).
Further, in the above clean preparation method of carboxymethyl nanocellulose material, the mass ratio of cellulose to alkali metal compound in step D is 1: (0.18-0.45); the swelling time of the cellulose is 0.5 to 3.0 hours, and the swelling temperature is 5 to 35 ℃.
Further, in the above clean preparation method of carboxymethyl nanocellulose material, the organic solvent in steps D and E is one of isopropanol, ethanol, isopropanol/ethanol, acetone, toluene, ethanol/toluene, isopropanol/toluene, and isobutanol.
Further, in the above clean preparation method of carboxymethyl nanocellulose material, the aqueous solution of organic solvent in step F is an ethanol/aqueous solution with a volume fraction of 70-90%.
Further, in the above clean preparation method of carboxymethyl nanocellulose material, the process parameters of the homogenization treatment in the step G are as follows: diluting the material with water to mass concentration of 2-5%, treating with homogenizer at 20000-45000psi, and homogenizing for 40-80 min.
The invention has the following beneficial effects:
1. the pulping process is pollution-free, the prepared pulp is excellent in quality, and three clean and efficient pulping technologies are adopted: the method comprises the steps of wood pre-dipping technology, high-energy mixed high-concentration bleaching oxygen pulping technology and continuous oxygen bleaching technology. Compared with the conventional high-pressure alkali boiling technology, the chlorine-free system is used as the presoaking agent, the emission of black liquor is reduced, the environmental pollution is greatly reduced, the mass transfer rate is accelerated by high-energy mixing, the speed of the bleaching reaction process is accelerated, the bleaching effect is improved, the oxygen bleaching is enhanced by using hydrogen peroxide, the hydrogen peroxide bleaching cost is greatly reduced, the purpose of reducing polymerization is achieved, the pressure on the environment is reduced, and the product quality is ensured.
2. The pulping method has strong applicability to raw materials, not only can use refined fiber products such as refined cotton, wood and the like, but also can use straws such as wheat, corn, straw, cotton and the like, reed, bagasse, fast-growing bamboo pulp and the like as pulping raw materials, and the prepared products meet the later-stage preparation requirements and provide a new utilization direction for a large amount of agricultural byproducts which are difficult to utilize.
3. An etherifying agent is added by a slurry method to prepare carboxymethyl cellulose, and then the carboxymethyl cellulose is directly diluted by water and then is introduced into a high-pressure homogenizer for homogenization treatment without drying to obtain nano-scale carboxymethyl cellulose nano-fibers CMNFs with controllable group content;
4. the invention adopts cellulose as raw material, uses chloroacetic acid as etherifying agent, determines the optimal proportion and process conditions of other components by controlling the feeding sequence, reaction temperature and reaction time, prepares carboxymethyl cellulose under safer and more reliable process conditions, and then introduces the carboxymethyl cellulose diluted by water into a high-pressure homogenizer for homogenization treatment to obtain the carboxymethyl cellulose nano-fiber CMNFs. The carboxymethyl cellulose nano-fiber prepared has the carboxymethyl substitution degree (namely DS) of 0.1 to 0.4, the diameter of 30 to 50nm and the length of 0.1 to 10 mu m. The prepared carboxymethyl cellulose nanofiber CMNFs has good hydrophilicity and material compatibility, and has very wide application prospect.
In conclusion, the invention prepares cellulose pulp by cleanly pulping by taking various straws and plant waste residues as raw materials, and then prepares the carboxymethyl cellulose nano-fiber CMNFs, thereby expanding the range of the raw materials for preparing the nano-cellulose, having simple and coherent process, environmental protection and low cost, opening up a new way for preparing the nano-cellulose and providing wide prospect for the application of the nano-cellulose. The method provided by the invention can be used for directly preparing the functional nano cellulose fiber by using cellulose as a raw material, the prepared modified nano cellulose contains carboxyl and has good crystallinity, and the prepared nano cellulose has small crystal grains, thereby providing a good foundation for later application of products.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly described below.
FIG. 1 is a transmission electron micrograph of a carboxymethyl cellulose nanofiber prepared in example 1 of the present invention;
FIG. 2 is an X-ray diffraction pattern of carboxymethyl cellulose nanofiber prepared in example 2 of the present invention;
FIG. 3 is an infrared spectrum of carboxymethyl cellulose nanofiber prepared in example 2 of the present invention.
Detailed Description
The present invention is further illustrated by the following specific examples. It should be noted that the embodiments described herein are merely preferred embodiments of the present invention, and are not intended to limit the present invention, and those skilled in the art may make various modifications and changes. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The percentages in examples 1 to 5 are, unless otherwise specified, mass percentages, and the component fractions are mass parts.
Example 1
Adding 40g of wheat straw powder crushed to 60 meshes into an aqueous solution containing 2% of sodium hydroxide, 0.4% of magnesium sulfate, 2% of lamina silicon, 0.1% of sodium citrate, 0.3% of methylene phosphonic acid and 0.1% of penetrating agent, presoaking for 60min at 40 ℃, and filtering for later use. Conveying the pre-soaked wheat straw powder to a mixer, and adding hydrogen peroxide with the concentration of 2%, sodium hydroxide with the concentration of 3%, and Na2SiO3、MgSO4And NaBH4Bleaching 2000g of bleaching solution I with the concentration of 2% for 1h, filtering the bleaching solution, feeding the filtered bleaching solution into a continuous oxygen bleaching machine, adding 300 parts of hydrogen peroxide with the concentration of 27.5%, 1 part of dicyandiamide catalyst, 60 parts of oxygen and 1 part of phenanthroline, bleaching for 1h, filtering and drying.
Under the condition of stirring, 12g of sodium hydroxide is added into 600g of isopropanol/water solution with the mass concentration of 85%, then 40g of wheat straw powder crushed to 60 meshes is added, the mixture reacts for l.5 hours at the temperature of 20 ℃, 13.5g of chloroacetic acid/ethanol solution containing 50% of chloroacetic acid is added, the temperature is increased to 50 ℃ for reaction for 1 hour, and the temperature is increased to 75 ℃ for reaction for 0.5 hour. After the reaction is finished, neutralizing with glacial acetic acid/ethanol solution, washing, centrifuging, diluting the material with water to 2.5% concentration, and homogenizing for 40min under the condition of 30000psi pressure by using a high-pressure homogenizer to obtain the carboxymethyl cellulose nano-fiber CMNFs.
Vacuum drying the obtained carboxymethyl cellulose nano-fiber CMNFs, and testing the carboxymethyl substitution degree to be 0.25 by a gray alkali method according to GB1904-2005 test standard; the carboxymethyl cellulose nano-fiber CMNFs is observed by a transmission electron microscope, and has the diameter of 40nm and the length of 800 nm.
Example 2
Adding 40g of cotton straw powder crushed to 60 meshes into an aqueous solution containing 2% of sodium hydroxide, 0.4% of magnesium sulfate, 3% of layered silicon, 0.1% of sodium citrate, 0.4% of methylene phosphonic acid and 0.1% of penetrating agent, presoaking for 50min at 50 ℃, and filtering for later use. The pre-soaked cotton straw powder is conveyed into a mixer, and hydrogen peroxide with the concentration of 3 percent, sodium hydroxide with the concentration of 4 percent and Na are added2SiO3、MgSO4And NaBH4Bleaching 2000g of bleaching solution I with the concentration of 2% for 1h, filtering the bleaching solution, feeding the filtered bleaching solution into a continuous oxygen bleaching machine, adding 300 parts of hydrogen peroxide with the concentration of 27.5%, 1 part of dicyandiamide catalyst, 60 parts of oxygen and 1 part of phenanthroline, bleaching for 1h, filtering and drying.
Under the condition of stirring, 15g of sodium hydroxide is added into 600g of isopropanol/water solution with the mass concentration of 85%, then 40g of cotton straw powder crushed to 60 meshes is added, the mixture reacts for 2 hours at the temperature of 20 ℃, 16.6g of chloroacetic acid/ethanol solution containing 50% chloroacetic acid is added, the temperature is increased to 50 ℃, the reaction is carried out for 1.5 hours, and the temperature is increased to 75 ℃ again for reaction for 0.5 hour. After the reaction is finished, neutralizing with glacial acetic acid/ethanol solution, washing, centrifuging, diluting the material with water to 2.0% concentration, and homogenizing for 50min under the condition of 30000psi pressure by using a high-pressure homogenizer to obtain the carboxymethyl cellulose nanofiber CMNFs.
Vacuum drying the obtained carboxymethyl cellulose nano-fiber CMNFs, and testing the carboxymethyl substitution degree to be 0.29 by a gray alkali method according to GB1904-2005 test standard; the carboxymethyl cellulose nanofiber CMNFs were observed by transmission electron microscopy, and had a diameter of 45nm and a length of 900 nm.
Example 3
Adding reed pulp 40g crushed to 50 meshes into aqueous solution containing sodium hydroxide 2%, magnesium sulfate 0.4%, silicon layer 2%, sodium citrate 0.1%, methylene phosphonic acid 0.5% and penetrating agent 0.1%, presoaking at 50 deg.C for 40min, and filtering for use. The pre-soaked cotton straw powder is conveyed into a mixer, and the mixture is added with 2 percent of hydrogen peroxide, 4 percent of sodium hydroxide and Na2SiO3、MgSO4And NaBH4Bleaching 2000g of bleaching solution I with the concentration of 2% for 1h, filtering the bleaching solution, feeding the filtered bleaching solution into a continuous oxygen bleaching machine, adding 300 parts of hydrogen peroxide with the concentration of 27.5%, 1 part of dicyandiamide catalyst, 60 parts of oxygen and 1 part of phenanthroline, bleaching for 1h, filtering and drying.
Under the condition of stirring, 12g of sodium hydroxide is added into 600g of isopropanol/water solution with the mass concentration of 85%, then 40g of reed pulp crushed to 50 meshes is added, the reaction is carried out for 2 hours at the temperature of 20 ℃, 13.0g of chloroacetic acid/ethanol solution containing 50% chloroacetic acid is added, the temperature is increased to 50 ℃, the reaction is carried out for 1.0 hour, and the temperature is increased to 75 ℃ again, and the reaction is carried out for 0.5 hour. After the reaction is finished, neutralizing with glacial acetic acid/ethanol solution, washing, centrifuging, diluting the material with water to 2.5% concentration, and homogenizing for 50min under the condition of 30000psi pressure by using a high-pressure homogenizer to obtain the carboxymethyl cellulose nanofiber CMNFs.
Vacuum drying the obtained carboxymethyl cellulose nano-fiber CMNFs, and testing the carboxymethyl substitution degree to be 0.27 by a gray alkali method according to GB1904-2005 test standard; the carboxymethyl cellulose nano-fiber CMNFs are observed by a transmission electron microscope, and have the diameter of 38nm and the length of 750 nm.
Example 4
Adding 40g of mixed pulp of reed and bagasse crushed to 50 meshes into aqueous solution containing 2% of sodium hydroxide, 0.5% of magnesium sulfate, 3% of layered silicon, 0.1% of sodium citrate, 0.5% of methylene phosphonic acid and 0.1% of penetrating agent, and presoaking at 50 DEG CAnd (4) filtering for 40min for later use. The pre-soaked reed and bagasse mixed slurry is conveyed into a mixer, and added with hydrogen peroxide with the concentration of 3 percent, sodium hydroxide with the concentration of 5 percent and Na2SiO3、MgSO4And NaBH4Bleaching 2000g of bleaching solution I with the concentration of 2% for 1h, filtering the bleaching solution, feeding the filtered bleaching solution into a continuous oxygen bleaching machine, adding 300 parts of hydrogen peroxide with the concentration of 27.5%, 1 part of dicyandiamide catalyst, 60 parts of oxygen and 1 part of phenanthroline, bleaching for 1h, filtering and drying.
Under the condition of stirring, 11g of sodium hydroxide is added into 600g of isopropanol/water solution with the mass concentration of 85%, 40g of reed and bagasse mixed slurry which is crushed to 50 meshes is added, the reaction is carried out for 2 hours at the temperature of 20 ℃, 12.0g of chloroacetic acid/ethanol solution containing 50% of chloroacetic acid is added, the temperature is increased to 50 ℃, the reaction is carried out for 1.0 hour, and the temperature is increased to 75 ℃ again for reaction for 0.5 hour. After the reaction is finished, neutralizing with glacial acetic acid/ethanol solution, washing, centrifuging, diluting the material with water to 2.5% concentration, and homogenizing for 50min under 25000psi by using a high-pressure homogenizer to obtain the carboxymethyl cellulose nanofiber CMNFs.
Vacuum drying the obtained carboxymethyl cellulose nano-fiber CMNFs, and testing the carboxymethyl substitution degree to be 0.24 by a grey alkali method according to GB1904-2005 test standard; the carboxymethyl cellulose nano-fiber CMNFs is observed by a transmission electron microscope, and has the diameter of 32nm and the length of 680 nm.
Example 5
40g of mixed slurry of the wheat straws and the corn straws crushed to 40 meshes is added into aqueous solution containing 2 percent of sodium hydroxide, 0.4 percent of magnesium sulfate, 2 percent of silicon, 0.1 percent of sodium citrate, 0.5 percent of methylene phosphonic acid and 0.1 percent of penetrating agent, and is presoaked for 40min at the temperature of 40 ℃ and filtered for standby application. Conveying the pre-soaked mixed slurry of wheat straw and corn straw to a mixer, and adding hydrogen peroxide with the concentration of 2%, sodium hydroxide with the concentration of 4%, and Na2SiO3、MgSO4And NaBH4Bleaching the bleaching solution I with the concentration of 2% for 1 hour in 2000g, filtering the bleaching solution, feeding the bleaching solution into a continuous oxygen bleaching machine, adding 300 parts of hydrogen peroxide with the concentration of 27.5%, 1 part of dicyandiamide catalyst, 60 parts of oxygen and 1 part of phenanthroline, and bleaching the bleaching solution II againFor 1h, then filtered and dried.
Under the condition of stirring, 15g of sodium hydroxide is added into 600g of isopropanol/water solution with the mass concentration of 85%, then 40g of mixed slurry of wheat straws and corn straws crushed to 40 meshes is added, the mixture reacts for 2 hours at the temperature of 20 ℃, 16.7g of chloroacetic acid/ethanol solution containing 50% of chloroacetic acid is added, the temperature is increased to 50 ℃, the reaction is carried out for 1.5 hours, and the temperature is increased to 75 ℃ again for reaction for 0.5 hour. After the reaction is finished, neutralizing with glacial acetic acid/ethanol solution, washing, centrifuging, diluting the material with water to 2.0% concentration, and homogenizing for 60min under the condition of 30000psi pressure by using a high-pressure homogenizer to obtain the carboxymethyl cellulose nanofiber CMNFs.
Vacuum drying the obtained carboxymethyl cellulose nano-fiber CMNFs, and testing the carboxymethyl substitution degree to be 0.26 by a grey alkali method according to GB1904-2005 test standard; the carboxymethyl cellulose nano-fiber CMNFs with the diameter of 49nm and the length of 1100nm is observed by a transmission electron microscope.
FIG. 1 is a Transmission Electron Micrograph (TEM) of the CMNFs prepared in example 1, from which it is clear that nanocelluloses having diameters between about 10 and 50nm and lengths in the nanometer to micrometer range are obtained, demonstrating that the process of the present invention produces nanocellulose fibers.
FIG. 2 is an X-ray diffraction pattern (XRD) of CMNFs prepared in example 2, and according to the data in the pattern, the crystallinity of the CMNFs is 45.3%, which proves that the material has good crystallinity.
FIG. 3 is an Infrared (IR) spectrum of CMNFs prepared in example 2, showing 1600cm of product-1The absorption vibration peak of COO-is shown, and the CMMFs are proved to contain carboxyl groups.
The above characterization proves that the method provided by the invention can be used for preparing the straw-based carboxymethyl cellulose nanofiber CMNFs by taking plant straws as raw materials, and the prepared carboxymethyl cellulose nanofiber CMNFs contain carboxyl and have good crystallinity, so that a good basis is provided for later application of products.
Claims (9)
1. A clean preparation method of carboxymethyl nano cellulose material is characterized by comprising the following steps:
A. pretreatment of raw materials: adding a cellulose raw material into a pre-soaking solution for pre-soaking and crushing;
B. the bleaching oxygen pulping technology comprises the following steps: concentrating the presoaked slurry, conveying the concentrated slurry to a mixer for mixing, and simultaneously adding bleaching liquor I to bleach the materials;
C. the continuous oxygen bleaching technology comprises the following steps: the pulp and the bleaching liquor II are conveyed to a continuous oxygen bleaching machine together by the mixer for bleaching again;
D. crushing and activating the slurry: crushing the pulp by a crusher, and swelling cellulose by an organic solvent and an alkali metal compound;
E. etherification: adding a mixture of an etherifying agent and an organic solvent, and etherifying at the temperature of 50-80 ℃;
F. neutralization and purification: neutralizing the base in the system with an acid; centrifuging the product, washing with water, and centrifuging again;
G. nano-crystallization: diluting the centrifugal material with water, and introducing the diluted centrifugal material into a high-pressure homogenizer for homogenization treatment to obtain carboxymethyl cellulose nanofibers;
the pre-immersion liquid in the step A comprises the following components in percentage by weight:
2% of alkali, 0.4-0.5% of magnesium sulfate, 2-3% of layer silicon, 0.1% of sodium citrate, 0.3-0.5% of methylene phosphonic acid, 0.1% of penetrating agent and the balance of water.
2. The clean preparation method of carboxymethyl nanocellulose material according to claim 1,
the cellulose raw material in the step A is one or a mixture of more of wheat straw, corn straw, rice straw, cotton straw, bamboo pulp, reed and bagasse, and the crushing granularity of the cellulose raw material is not more than 50 meshes.
3. The clean preparation method of carboxymethyl nanocellulose material according to claim 1,
the presoaking temperature in the step A is 40-50 ℃, and the presoaking time is 40-60 min.
4. The clean preparation method of carboxymethyl nanocellulose material according to claim 1,
the bleaching liquor I in the step B consists of the following components:
hydrogen peroxide, alkali and Na2SiO3、MgSO4、NaBH4And water.
5. The clean preparation method of carboxymethyl nanocellulose material according to claim 4,
the bleaching liquor I in the step B consists of the following components in percentage by mass: 2-5% of hydrogen peroxide, 3-5% of alkali and 2% of Na2SiO3、MgSO4And NaBH4The bleaching agent and the balance of water.
6. The clean preparation method of carboxymethyl nanocellulose material according to claim 1,
the bleaching liquor II in the step C consists of the following components in parts by weight:
300 parts of 27.5% hydrogen peroxide, 1 part of dicyandiamide catalyst, 60 parts of oxygen and 1 part of phenanthroline.
7. The clean preparation method of carboxymethyl nanocellulose material according to claim 1,
the etherifying agent in the step E is an organic solvent of chloroacetic acid with the mass fraction of 40-60%, and the etherification time is 1-4 hours; and D, the mass ratio of the cellulose pulp obtained in the step D to the chloroacetic acid is 1: (0.20-0.50);
the mass ratio of the cellulose to the alkali metal compound in the step D is 1: (0.18-0.45); the swelling time of the cellulose is 0.5 to 3.0 hours, and the swelling temperature is 5 to 35 ℃.
8. The clean preparation method of carboxymethyl nanocellulose material according to claim 1,
the organic solvent in the steps D and E is one of isopropanol, ethanol, isopropanol/ethanol, acetone, toluene, ethanol/toluene, isopropanol/toluene and isobutanol; and F, the aqueous solution of the organic solvent is an ethanol/aqueous solution with the volume fraction of 70-90%.
9. The clean preparation method of carboxymethyl nanocellulose material according to claim 1,
the process parameters of the homogenization treatment in the step G are as follows: diluting the material with water to mass concentration of 2-5%, treating with homogenizer at 20000-45000psi, and homogenizing for 40-80 min.
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| CN110357973A (en) * | 2018-04-10 | 2019-10-22 | 上海长光企业发展有限公司 | A kind of sodium carboxymethylcellulose and its preparation method and application |
| CN111019005A (en) * | 2019-12-13 | 2020-04-17 | 华南理工大学 | Method for preparing carboxylated nanocellulose by using citric acid hydrolysis and combining catalyst and ultrasonic-assisted two-step process |
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