CN111171337A - Preparation method of acetylated lignocellulose - Google Patents
Preparation method of acetylated lignocellulose Download PDFInfo
- Publication number
- CN111171337A CN111171337A CN202010103658.0A CN202010103658A CN111171337A CN 111171337 A CN111171337 A CN 111171337A CN 202010103658 A CN202010103658 A CN 202010103658A CN 111171337 A CN111171337 A CN 111171337A
- Authority
- CN
- China
- Prior art keywords
- solid
- solution
- wood fiber
- raw material
- washing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
Abstract
The invention provides a preparation method of acetylated wood fibers, which comprises the following steps: (1) impregnating a wood fiber raw material with an alkaline salt solution, and washing a solid after solid-liquid separation to obtain an impregnation liquid and an impregnation material; (2) mixing glacial acetic acid solution with the impregnating material obtained in the step (1), and carrying out acetylation reaction under the action of a molecular sieve solid acid catalyst to obtain acetylated wood fibers. The preparation method of the acetylated wood fiber provided by the invention can improve the acetyl content in the wood fiber, enables the acetyl substitution degree to reach 0.8, is beneficial to the subsequent utilization of the acetylated wood fiber, and has the advantages of simple operation and low consumption of organic solvent.
Description
Technical Field
The invention belongs to the technical field of biomass utilization, relates to a method for treating functional cellulose, and particularly relates to a method for preparing acetylated lignocellulose.
Background
China is a large country for fiber production, the annual output reaches more than 4900 ten thousand tons, and the produced fiber types comprise terylene, chinlon, acrylic fiber, cellulose fiber and the like. The fiber has wide application field, is often applied to the aspects of prevention and treatment, medicine, electricity, civil engineering and the like, and influences the aspects of daily life.
Besides daily life, part of special fibers subjected to special treatment can be applied to more advanced fields. The special fiber is made by high and new technology, and has special physical and chemical structure, performance and use, or has special function. The types of the fiber mainly comprise high-performance fiber, high-functional fiber and high-sensitivity fiber.
The wood fiber material is a material with components including cellulose, hemicellulose, lignin and the like, has a structure containing a large amount of hydroxyl groups, is strong in hydrophilic capacity and easy to absorb water, and is not beneficial to popularization and application, for example, wood fibers which are easy to absorb water are easy to expand with heat and contract with cold to cause wood blocks to deform, crack and breed bacteria; moreover, the structure of the wood fiber contains more hydroxyl groups and has strong hydrophilic capability, so that the wood fiber is not good in compatibility with resin, and finally the performance of the material is influenced. Therefore, the wood fiber is modified, the number of hydroxyl groups in the structure of the wood fiber is reduced, the water absorption of the wood fiber is reduced, the antibacterial property and the resin compatibility of the wood fiber are enhanced, and the wood fiber is beneficial to popularization and application.
When the lignocellulose material is subjected to acylation reaction, hydroxyl groups in the structure of the lignocellulose material are replaced by acetyl groups, and the acetyl groups do not have hydrophilicity, so that the hydrophilicity and the water absorption capacity of the lignocellulose material are reduced after the acylation modification. Meanwhile, the volume of the acetyl is larger than that of a hydrogen atom, and after acylation modification, cell walls in the wood fiber material and pore passages between the cell walls are blocked by the large-volume acetyl, so that water molecules are prevented from permeating into the wood fiber material, and the water absorption capacity of the wood fiber material is remarkably reduced.
CN 102802894a discloses an esterified lignocellulosic material and a method for its manufacture, the method comprising: the method is characterized in that the solid wood is soaked in the soaking liquid containing acetic anhydride, the soaked solid wood is contacted with hot steam to heat the soaked solid wood to form acetylated solid wood, the steam comprises acetyl compounds selected from acetic anhydride or acetic acid, although the method can perform acetylation modification on the wood, the method uses both the solution containing acetic anhydride and the steam containing acetic anhydride, the consumption of organic solvent is high, and the method is not beneficial to energy conservation and environmental protection.
CN 102964605a discloses an esterification modification method of lignocellulosic biomass, which comprises: firstly, drying and crushing the wood fiber biomass; then carrying out pre-ball milling; then adding an esterification reagent, and continuing ball milling to perform esterification modification reaction; and (4) washing and drying the product after the reaction is finished, and remembering to obtain the esterification modified product of the wood fiber biomass. But the ball milling has a great influence on the appearance of the wood fiber biomass.
CN 105367667a discloses a method for simultaneously preparing acetylated wood fiber materials with different appearance characteristics, which utilizes two containers which are separated by a partition plate and are communicated up and down, places a thicker wood fiber material in a first container, and adds liquid acetic anhydride until the wood fiber material is immersed; and placing the finer wood fiber material in a second container, adding the wood fiber material into the first container to enable the wood fiber material and liquid acetic anhydride to perform acylation reaction, and diffusing gaseous acetic anhydride generated by boiling through small holes of the intermediate partition plate to perform acylation reaction with the wood fiber material in the second container. The method also needs more liquid acetic anhydride, and a large amount of acetic anhydride vapor solution causes air pollution, which is not beneficial to energy conservation and environmental protection.
Therefore, the method for improving the substitution degree of the acetyl group of the wood fiber is provided, has low consumption of organic solvent, is simple and convenient to operate, and has positive significance for reducing the cost of acetylation of the wood fiber and reducing the pollution degree of acetylation of the wood fiber to the environment.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the preparation method of the acetylated wood fiber, which has the advantages of simple process and convenient operation, can ensure that the substitution degree of the acetyl group of the fiber reaches 0.8, and ensures that the prepared acetylated wood fiber is more simply used for subsequent application.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of acetylated wood fibers, which comprises the following steps:
(1) impregnating a wood fiber raw material with an alkaline salt solution, and washing a solid after solid-liquid separation to obtain an impregnation liquid and an impregnation material;
(2) mixing glacial acetic acid solution with the impregnating material in the step (1), and performing acetylation reaction under the action of a molecular sieve solid acid catalyst to obtain acetylated wood fibers.
The method firstly uses alkaline salt to impregnate the crushed wood fiber raw material, so that the fiber raw material is swelled, thereby being beneficial to the permeation of organic acid in the acetylation process and improving the acetylation reaction effect. And the addition of the alkaline salt is beneficial to reducing silicon in the wood fiber raw material and the wide application of the prepared acetylated wood fiber.
Preferably, the alkaline salt solution in step (1) comprises any one or a combination of at least two of a carbonate solution, an acetate solution or a sulfite solution, and typical but non-limiting combinations include a carbonate solution and an acetate solution, an acetate solution and a sulfite solution, a carbonate solution and a sulfite solution or a carbonate solution, an acetate solution and a sulfite solution, preferably an acetate solution.
Preferably, the carbonate solution comprises a sodium carbonate solution and/or a potassium carbonate solution.
Preferably, the acetate solution comprises a sodium acetate solution and/or a potassium acetate solution.
Preferably, the sulfite solution comprises a sodium sulfite solution and/or a potassium sulfite solution.
Preferably, the alkaline salt solution of step (1) has a mass concentration of 5 to 50 wt.%, for example 5 wt.%, 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.% or 50 wt.%, but not limited to the recited values, and other values not recited within the range of values are equally applicable, preferably 15 to 30 wt.%.
Preferably, the lignocellulosic feedstock of step (1) comprises woody biomass and/or graminaceous biomass.
Preferably, the woody biomass comprises any one or a combination of at least two of hardwood, softwood, or shrub, and may be, for example, a combination of hardwood and softwood, a combination of softwood and shrub, a combination of hardwood and shrub, or a combination of hardwood, softwood, and shrub.
Preferably, the graminaceous biomass comprises any one or a combination of at least two of bagasse, bamboo, rice straw, wheat straw, corn stover, or reed, typical but non-limiting combinations include bagasse and bamboo, bamboo and rice straw, rice straw and wheat straw, wheat straw and corn stover, corn stover and reed, wheat straw, corn stover and reed, bamboo, rice straw and wheat straw, or bagasse, bamboo, rice straw, wheat straw, corn stover and reed.
Preferably, the mass ratio of the alkaline salt solution to the lignocellulosic feedstock in step (1) is (2-15):1, and may be, for example, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1 or 15:1, but is not limited to the recited values, and other values not recited within the range of values are equally applicable, preferably (8-12): 1.
Preferably, the impregnation in step (1) is carried out at a temperature of 60 to 150 ℃, for example 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃, but not limited to the values recited, and other values not recited within the range of values are equally applicable, preferably 70 to 100 ℃.
Preferably, the pressure of the impregnation in step (1) is 0.1 to 0.2MPa, and may be, for example, 0.1MPa, 0.12MPa, 0.14MPa, 0.16MPa, 0.18MPa or 0.2MPa, but is not limited to the values recited, and other values not recited within the range of values are equally applicable, preferably 0.12 to 0.18 MPa.
Preferably, the impregnation in step (1) is carried out for a period of time of 1 to 5 hours, for example 1 hour, 2 hours, 3 hours, 4 hours or 5 hours, but not limited to the values cited, and other values not listed within the range of values are equally applicable, preferably 2 to 3 hours.
Preferably, the washing in step (1) is washing with water.
Preferably, the mass ratio of the amount of water used for washing to the solid after solid-liquid separation is (2-10):1, and may be, for example, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, but is not limited to the values listed, and other values not listed in the numerical range are also applicable, and (4-6):1 is preferred.
Preferably, the number of washes in step (1) is 3 to 20, and may be, for example, 3, 5, 8, 10, 12, 14, 15, 16, 18 or 20, but is not limited to the recited values, and other values not recited within the range of values are equally applicable, preferably 5 to 8.
Preferably, the method further comprises the step of concentrating the impregnated solution and the washed washing solution to recover water, and the recovered concentrated solution can be subjected to conventional crystallization treatment to obtain a byproduct silicate, so that the economic benefit of an enterprise is improved.
Preferably, the mass ratio of the wood fiber raw material in the step (1) to the glacial acetic acid solution in the step (2) is 1 (2-20), and can be 1:2, 1:4, 1:6, 1:8, 1:10, 1:12, 1:14, 1:16, 1:18 or 1:20, but is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable, and are preferably 1 (8-12).
Preferably, the carrier of the molecular sieve solid acid catalyst in the step (2) is titanium dioxide.
According to the invention, a titanium dioxide molecular sieve solid acid catalyst is selected to catalyze acetylation reaction, so that the acetyl content in the wood fiber is increased, the degree of substitution of the acetyl of the fiber can reach 0.8, and the application field of the wood fiber is enhanced.
Preferably, the acetylation reaction of step (2) is carried out under stirring, and the molecular sieve solid acid catalyst is fixed on a stirring paddle used for stirring.
Preferably, the temperature of the acetylation reaction in step (2) is 60 to 150 ℃, and may be, for example, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃, but is not limited to the recited values, and other values not recited in the range of values are equally applicable, preferably 80 to 120 ℃.
Preferably, the acetylation reaction in step (2) is carried out for 1-10h, such as 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h, but not limited to the recited values, and other values not recited in the range of values are equally applicable, preferably 2-4 h.
Preferably, the preparation method further comprises the step of pretreating the lignocellulosic feedstock of step (1): cutting the comminuted lignocellulosic feedstock such that the lignocellulosic feedstock has a length of less than or equal to 5cm, and may be, for example, 1cm, 2cm, 3cm, 4cm or 5cm, but is not limited to the recited values, and other values within the recited ranges are equally applicable; a width of ≦ 5cm, which may be, for example, 1cm, 2cm, 3cm, 4cm or 5cm, but is not limited to the values listed, and other values not listed within the numerical range are equally applicable; the thickness is less than or equal to 2cm, for example 0.5cm, 0.8cm, 1cm, 1.5cm or 2cm, but is not limited to the values listed, and other values not listed in the numerical ranges are equally applicable. The cutting and crushing are performed by using a cutting and crushing machine, and a person skilled in the art can select a proper model according to the process requirements, and the invention is not limited too much.
The larger the specific surface area of the lignocellulosic feedstock, the higher the impregnation effect, but the higher the treatment costs. The invention comprehensively considers the processing difficulty and the dipping effect, and the invention pretreats the wood fiber raw material to ensure that the length is less than or equal to 5cm, the width is less than or equal to 5cm and the thickness is less than or equal to 2 cm.
Preferably, the preparation method further comprises the step of performing ball milling treatment on the cut and crushed wood fiber raw material, wherein the size of the wood fiber raw material can be further reduced through the ball milling treatment, and the specific surface area of the wood fiber raw material is increased, so that the impregnation effect is improved.
Preferably, the preparation method further comprises the step of post-treating the acetylated wood fibers obtained in the step (2): and (3) cooking the acetylated wood fibers obtained in the step (2) by using an organic acid, and washing after solid-liquid separation.
Preferably, the organic acid comprises any one of, or a combination of at least two of, propionic acid, n-butyric acid or isobutyric acid, typical but non-limiting combinations include a combination of propionic acid and n-butyric acid, n-butyric acid and isobutyric acid, propionic acid and isobutyric acid or a combination of propionic acid, n-butyric acid and isobutyric acid, preferably a combination of n-butyric acid and isobutyric acid.
Preferably, the mass ratio of the added amount of the organic acid to the glacial acetic acid solution in the step (2) is 1 (5-20), and the organic acid may be, for example, 1:5, 1:6, 1:8, 1:10, 1:12, 1:14, 1:16, 1:18 or 1:20, but is not limited to the enumerated values, and other unrecited values within the numerical range are also applicable, and are preferably 1 (8-12).
Preferably, the cooking temperature is 100-200 ℃, for example 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ or 200 ℃, but not limited to the recited values, and other values within the range of values are equally applicable, preferably 140-160 ℃.
Preferably, the cooking pressure is 0.1 to 0.2MPa, and may be, for example, 0.1MPa, 0.12MPa, 0.14MPa, 0.15MPa, 0.16MPa, 0.18MPa or 0.2MPa, but is not limited to the values recited, and other values not recited within the range of values are equally applicable, preferably 0.12 to 0.16 MPa.
Preferably, the cooking time is 2 to 10 hours, for example 2, 3, 4, 5, 6, 7, 8, 9 or 10 hours, but not limited to the recited values, and other values not recited in the range of values are equally applicable, preferably 4 to 6 hours.
Preferably, the washing is performed by using glacial acetic acid and then water.
Preferably, the mass ratio of the glacial acetic acid used for the glacial acetic acid washing to the solid after the solid-liquid separation is (2-10):1, and may be, for example, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, but is not limited to the enumerated values, and other unrecited values within the numerical range are equally applicable, and preferably (4-6): 1.
Preferably, the number of glacial acetic acid washes is 3 to 20, for example 3, 4, 6, 8, 10, 12, 14, 15, 16, 18 or 20, but is not limited to the values listed, and other values not listed in the numerical range are equally applicable, preferably 4 to 8.
Preferably, the mass ratio of water used for water washing to solid after solid-liquid separation is (2-10):1, and may be, for example, 2:1, 4:1, 6:1, 8:1 or 10:1, but is not limited to the enumerated values, and other values not enumerated within the numerical range are also applicable, and preferably (4-6): 1.
Preferably, the number of water washes is 3 to 20, for example 3, 4, 6, 8, 10, 12, 14, 15, 16, 18 or 20, but not limited to the values listed, and other values not listed within the range of values are equally applicable, preferably 4 to 8.
And (3) carrying out solid-liquid separation to obtain a cooking liquid and a solid, and washing the solid to obtain the acetylated wood fiber. The cooking liquor and the glacial acetic acid washing liquid are combined and then the organic acid in the cooking liquor is recovered, so that the cost is saved, and the purposes of energy conservation and emission reduction are achieved.
As a preferable technical scheme of the preparation method, the preparation method comprises the following steps:
(1) soaking the cut and crushed wood fiber raw material for 1-5h at 60-150 ℃ and 0.1-0.2MPa by using an alkaline salt solution with the mass concentration of 5-50 wt%, wherein the mass ratio of the alkaline salt solution to the wood fiber raw material is (2-15):1, and washing the solid after solid-liquid separation to obtain a soaking solution and a soaking material;
(2) mixing a glacial acetic acid solution with the impregnation material obtained in the step (1), wherein the mass ratio of the wood fiber raw material in the step (1) to the glacial acetic acid solution in the step (2) is 1 (2-20), and performing acetylation reaction under the action of a titanium dioxide molecular sieve solid acid catalyst, wherein the temperature of the acetylation reaction is 60-150 ℃ and the time is 1-10h to obtain an acetylated wood fiber raw material;
(3) cooking the acetylated wood fiber obtained in the step (2) for 2-10h at 100-200 ℃ and 0.1-0.2MPa by using organic acid, wherein the mass ratio of the addition amount of the organic acid to the glacial acetic acid solution in the step (2) is 1 (5-20); after solid-liquid separation, the solid-liquid separation is washed by glacial acetic acid and then by water.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
(1) the wood fiber raw material can be swelled through alkaline salt impregnation, so that organic acid is easier to permeate in the subsequent acetylation reaction process, the acetylation reaction effect is better, and silicon in the raw material can be dissolved out through alkaline salt solution preimpregnation;
(2) according to the invention, the immobilized molecular sieve is used for catalyzing acetylation of the wood fiber raw material, so that on one hand, the catalytic efficiency and the recovery rate of the molecular sieve catalyst are improved, on the other hand, only an acetic acid solvent is used for acetylating the wood fiber, the usage amount of a reagent is reduced, the acetyl content in the wood fiber is improved, and the degree of substitution of the acetyl of the fiber reaches 0.8;
(3) the cooking liquor and the fiber pickling liquor which are filtered and separated after cooking can recover the organic acid in the cooking liquor, so that the organic acid can be reused in acetylation, cooking and fiber washing, and the utilization rate of reagents is improved.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The present embodiment provides a method for preparing acetylated wood fibers, comprising the following steps:
(1) soaking the cut and crushed wood fiber raw material for 2.5 hours at 80 ℃ and 0.15MPa by using a sodium acetate solution with the mass concentration of 20 wt%, wherein the mass ratio of the sodium acetate solution to the wood fiber raw material is 10:1, and washing the solid for 6 times by using water after solid-liquid separation to obtain a soaking solution and a soaking material; concentrating the impregnation liquid, recovering water, and using the concentrated solution to obtain a byproduct sodium silicate; the wood fiber raw material is wheat straw; the length, the width and the thickness of the cut and crushed wood fiber raw material are less than or equal to 5cm, less than or equal to 5cm and less than or equal to 2cm respectively;
(2) mixing a glacial acetic acid solution with the impregnating material obtained in the step (1), wherein the mass ratio of the wood fiber raw material in the step (1) to the glacial acetic acid solution in the step (2) is 10:1, and carrying out acetylation reaction under the stirring action of a stirring paddle fixed with a titanium dioxide molecular sieve solid acid catalyst, wherein the acetylation reaction temperature is 100 ℃ and the acetylation reaction time is 3 hours, so as to obtain acetylated wood fibers.
Example 2
The present embodiment provides a method for preparing acetylated wood fibers, comprising the following steps:
(1) soaking the cut and crushed wood fiber raw material for 2 hours at 100 ℃ and 0.12MPa by using a potassium acetate solution with the mass concentration of 30 wt%, wherein the mass ratio of the potassium acetate solution to the wood fiber raw material is 8:1, and washing the solid for 5 times by using water after solid-liquid separation to obtain a soaking solution and a soaking material; concentrating the impregnation liquid, recovering water, and using the concentrated solution to obtain a byproduct sodium silicate; the wood fiber raw material is straw; the length, the width and the thickness of the cut and crushed wood fiber raw material are less than or equal to 5cm, less than or equal to 5cm and less than or equal to 2cm respectively;
(2) mixing a glacial acetic acid solution with the impregnating material obtained in the step (1), wherein the mass ratio of the wood fiber raw material in the step (1) to the glacial acetic acid solution in the step (2) is 8:1, and carrying out acetylation reaction under the stirring action of a stirring paddle fixed with a titanium dioxide molecular sieve solid acid catalyst, wherein the acetylation reaction temperature is 80 ℃ and the acetylation reaction time is 4 hours, so as to obtain acetylated wood fibers.
Example 3
The present embodiment provides a method for preparing acetylated wood fibers, comprising the following steps:
(1) soaking the cut and crushed wood fiber raw material for 3 hours at 70 ℃ and 0.18MPa by using a sodium carbonate solution with the mass concentration of 15 wt%, wherein the mass ratio of the sodium carbonate solution to the wood fiber raw material is 12:1, and washing the solid for 8 times by using water after solid-liquid separation to obtain a soaking solution and a soaking material; concentrating the impregnation liquid, recovering water, and using the concentrated solution to obtain a byproduct sodium silicate; the wood fiber raw material is corn straw; the length, the width and the thickness of the cut and crushed wood fiber raw material are less than or equal to 5cm, less than or equal to 5cm and less than or equal to 2cm respectively;
(2) mixing a glacial acetic acid solution with the impregnation material obtained in the step (1), wherein the mass ratio of the wood fiber raw material in the step (1) to the glacial acetic acid solution in the step (2) is 12:1, and carrying out acetylation reaction under the stirring action of a stirring paddle fixed with a titanium dioxide molecular sieve solid acid catalyst, wherein the acetylation reaction temperature is 120 ℃ and the acetylation reaction time is 2 hours, so as to obtain acetylated wood fibers.
Example 4
The present embodiment provides a method for preparing acetylated wood fibers, comprising the following steps:
(1) soaking the cut, crushed and ball-milled wood fiber raw material for 5 hours at 150 ℃ and 0.2MPa by using a potassium carbonate solution with the mass concentration of 5 wt%, wherein the mass ratio of the potassium carbonate solution to the wood fiber raw material is 15:1, and washing the solid for 3 times by using water after solid-liquid separation to obtain a soaking solution and a soaking material; concentrating the impregnation liquid, recovering water, and using the concentrated solution to obtain a byproduct sodium silicate; the wood fiber raw material is bamboo; the length, the width and the thickness of the wood fiber raw material after cutting, crushing and ball milling are less than or equal to 5cm, 5cm and 2cm respectively;
(2) mixing a glacial acetic acid solution with the impregnation material obtained in the step (1), wherein the mass ratio of the wood fiber raw material in the step (1) to the glacial acetic acid solution in the step (2) is 20:1, and carrying out acetylation reaction under the stirring action of a stirring paddle fixed with a titanium dioxide molecular sieve solid acid catalyst, wherein the acetylation reaction temperature is 60 ℃ and the acetylation reaction time is 10 hours, so as to obtain acetylated wood fibers.
Example 5
The present embodiment provides a method for preparing acetylated wood fibers, comprising the following steps:
(1) soaking the cut and crushed wood fiber raw material for 1 hour at 60 ℃ and 0.1MPa by using a sodium sulfite solution with the mass concentration of 50 wt%, wherein the mass ratio of the sodium sulfite solution to the wood fiber raw material is 2:1, and washing the solid for 20 times by using water after solid-liquid separation to obtain a soaking solution and a soaking material; concentrating the impregnation liquid, recovering water, and using the concentrated solution to obtain a byproduct sodium silicate; the wood fiber raw material is reed; the length, the width and the thickness of the cut and crushed wood fiber raw material are less than or equal to 5cm, less than or equal to 5cm and less than or equal to 2cm respectively;
(2) mixing a glacial acetic acid solution with the impregnation material obtained in the step (1), wherein the mass ratio of the wood fiber raw material in the step (1) to the glacial acetic acid solution in the step (2) is 2:1, and carrying out acetylation reaction under the stirring action of a stirring paddle fixed with a titanium dioxide molecular sieve solid acid catalyst, wherein the acetylation reaction temperature is 150 ℃ and the acetylation reaction time is 1h, so as to obtain acetylated wood fibers.
Example 6
The present embodiment provides a method for preparing acetylated wood fibers, comprising the following steps:
(1) cutting the crushed wood fiber raw material for 2.5 hours at 80 ℃ and 0.15MPa by using a sodium acetate solution with the mass concentration of 20 wt%, wherein the mass ratio of the sodium acetate solution to the wood fiber raw material is 10:1, and washing the solid for 6 times by using water after solid-liquid separation to obtain an impregnation liquid and an impregnation material; concentrating the impregnation liquid, recovering water, and using the concentrated solution to obtain a byproduct sodium silicate; the wood fiber raw material is wheat straw; the length, the width and the thickness of the cut and crushed wood fiber raw material are less than or equal to 5cm, less than or equal to 5cm and less than or equal to 2cm respectively;
(2) mixing a glacial acetic acid solution with the impregnation material obtained in the step (1), wherein the mass ratio of the wood fiber raw material in the step (1) to the glacial acetic acid solution in the step (2) is 10:1, and performing acetylation reaction under the stirring action of a stirring paddle fixed with a titanium dioxide molecular sieve solid acid catalyst, wherein the acetylation reaction temperature is 100 ℃ and the acetylation reaction time is 3 hours, so as to obtain an acetylated wood fiber raw material;
(3) cooking the acetylated wood fiber raw material obtained in the step (2) for 5 hours at 150 ℃ and 0.15MPa by using n-butyric acid, wherein the mass ratio of the addition amount of the n-butyric acid to the glacial acetic acid solution in the step (2) is 1: 10; after solid-liquid separation, firstly washing for 6 times by using glacial acetic acid, and then washing for 6 times by using water, wherein the mass ratio of the dosage of the glacial acetic acid to the solid after the solid-liquid separation is 5:1, the mass ratio of the dosage of the water to the solid after the solid-liquid separation is 5:1, and the solid after washing is a post-treatment product.
Example 7
The present embodiment provides a method for preparing acetylated wood fibers, comprising the following steps:
(1) soaking the cut and crushed wood fiber raw material for 2 hours at 100 ℃ and 0.12MPa by using a potassium acetate solution with the mass concentration of 30 wt%, wherein the mass ratio of the potassium acetate solution to the wood fiber raw material is 8:1, and washing the solid for 5 times by using water after solid-liquid separation to obtain a soaking solution and a soaking material; concentrating the impregnation liquid, recovering water, and using the concentrated solution to obtain a byproduct sodium silicate; the wood fiber raw material is straw; the length, the width and the thickness of the cut and crushed wood fiber raw material are less than or equal to 5cm, less than or equal to 5cm and less than or equal to 2cm respectively;
(2) mixing a glacial acetic acid solution with the impregnation material obtained in the step (1), wherein the mass ratio of the wood fiber raw material in the step (1) to the glacial acetic acid solution in the step (2) is 8:1, and performing acetylation reaction under the stirring action of a stirring paddle fixed with a titanium dioxide molecular sieve solid acid catalyst, wherein the acetylation reaction temperature is 80 ℃ and the acetylation reaction time is 4 hours, so as to obtain an acetylated wood fiber raw material;
(3) digesting the acetylated wood fiber raw material obtained in the step (2) for 6 hours at 140 ℃ and 0.16MPa by using propionic acid, wherein the mass ratio of the addition amount of the propionic acid to the glacial acetic acid solution in the step (2) is 1: 12; after solid-liquid separation, firstly washing for 4 times by using glacial acetic acid, and then washing for 8 times by using water, wherein the mass ratio of the dosage of the glacial acetic acid to the solid after the solid-liquid separation is 6:1, the mass ratio of the dosage of the water to the solid after the solid-liquid separation is 4:1, and the solid after washing is a post-treatment product.
Example 8
The present embodiment provides a method for preparing acetylated wood fibers, comprising the following steps:
(1) soaking the cut and crushed wood fiber raw material for 3 hours at 70 ℃ and 0.18MPa by using a sodium carbonate solution with the mass concentration of 15 wt%, wherein the mass ratio of the sodium carbonate solution to the wood fiber raw material is 12:1, and washing the solid for 8 times by using water after solid-liquid separation to obtain a soaking solution and a soaking material; concentrating the impregnation liquid, recovering water, and using the concentrated solution to obtain a byproduct sodium silicate; the wood fiber raw material is corn straw; the length, the width and the thickness of the cut and crushed wood fiber raw material are less than or equal to 5cm, less than or equal to 5cm and less than or equal to 2cm respectively;
(2) mixing a glacial acetic acid solution with the impregnation material obtained in the step (1), wherein the mass ratio of the wood fiber raw material in the step (1) to the glacial acetic acid solution in the step (2) is 12:1, and performing acetylation reaction at the temperature of 120 ℃ for 2 hours under the stirring action of a stirring paddle fixed with a titanium dioxide molecular sieve solid acid catalyst to obtain an acetylated wood fiber raw material;
(3) boiling the acetylated wood fiber raw material obtained in the step (2) for 4h at 160 ℃ and 0.12MPa by using isobutyric acid, wherein the mass ratio of the addition amount of the isobutyric acid to the glacial acetic acid solution in the step (2) is 1: 8; after solid-liquid separation, firstly washing with glacial acetic acid for 8 times, and then washing with water for 4 times, wherein the mass ratio of the dosage of the glacial acetic acid to the solid after solid-liquid separation is 4:1, the mass ratio of the dosage of the water to the solid after solid-liquid separation is 6:1, and the solid after washing is a post-treatment product.
Example 9
The present embodiment provides a method for preparing acetylated wood fibers, comprising the following steps:
(1) soaking the cut and crushed wood fiber raw material for 5 hours at 150 ℃ and 0.2MPa by using a potassium carbonate solution with the mass concentration of 5 wt%, wherein the mass ratio of the potassium carbonate solution to the wood fiber raw material is 15:1, and washing the solid for 3 times by using water after solid-liquid separation to obtain a soaking solution and a soaking material; concentrating the impregnation liquid, recovering water, and using the concentrated solution to obtain a byproduct sodium silicate; the wood fiber raw material is bamboo; the length, the width and the thickness of the cut and crushed wood fiber raw material are less than or equal to 5cm, less than or equal to 5cm and less than or equal to 2cm respectively;
(2) mixing a glacial acetic acid solution with the impregnation material obtained in the step (1), wherein the mass ratio of the wood fiber raw material in the step (1) to the glacial acetic acid solution in the step (2) is 20:1, and performing acetylation reaction under the stirring action of a stirring paddle fixed with a titanium dioxide molecular sieve solid acid catalyst, wherein the acetylation reaction temperature is 60 ℃ and the acetylation reaction time is 10 hours, so as to obtain an acetylated wood fiber raw material;
(3) cooking the acetylated wood fiber raw material obtained in the step (2) for 2h at 200 ℃ and 0.1MPa by using mixed acid of n-butyric acid and isobutyric acid in a mass ratio of 1:1, wherein the mass ratio of the addition amount of the mixed acid to the glacial acetic acid solution in the step (2) is 1: 5; after solid-liquid separation, firstly washing for 3 times by using glacial acetic acid, and then washing for 3 times by using water, wherein the mass ratio of the dosage of the glacial acetic acid to the solid after the solid-liquid separation is 10:1, the mass ratio of the dosage of the water to the solid after the solid-liquid separation is 10:1, and the solid after washing is a post-treatment product.
Example 10
The present embodiment provides a method for preparing acetylated wood fibers, comprising the following steps:
(1) soaking the cut and crushed wood fiber raw material for 1 hour at 60 ℃ and 0.1MPa by using a sodium sulfite solution with the mass concentration of 50 wt%, wherein the mass ratio of the sodium sulfite solution to the wood fiber raw material is 2:1, and washing the solid for 20 times by using water after solid-liquid separation to obtain a soaking solution and a soaking material; concentrating the impregnation liquid, recovering water, and using the concentrated solution to obtain a byproduct sodium silicate; the wood fiber raw material is reed; the length, the width and the thickness of the cut and crushed wood fiber raw material are less than or equal to 5cm, less than or equal to 5cm and less than or equal to 2cm respectively;
(2) mixing a glacial acetic acid solution with the impregnation material obtained in the step (1), wherein the mass ratio of the wood fiber raw material in the step (1) to the glacial acetic acid solution in the step (2) is 2:1, and performing acetylation reaction at the temperature of 150 ℃ for 1h under the stirring action of a stirring paddle fixed with a titanium dioxide molecular sieve solid acid catalyst to obtain acetylated wood fibers;
(3) cooking the acetylated wood fiber raw material obtained in the step (2) for 10 hours at 100 ℃ and 0.2MPa by using mixed acid of n-butyric acid and isobutyric acid in a mass ratio of 1:1, wherein the mass ratio of the addition amount of the mixed acid to the glacial acetic acid solution in the step (2) is 1: 20; after solid-liquid separation, firstly washing for 20 times by using glacial acetic acid, and then washing for 20 times by using water, wherein the mass ratio of the dosage of the glacial acetic acid to the solid after the solid-liquid separation is 2:1, the mass ratio of the dosage of the water to the solid after the solid-liquid separation is 2:1, and the solid after washing is a post-treatment product.
Example 11
This example provides a process for the preparation of acetylated wood fibres, identical to example 1 except that the impregnation temperature in step (1) is 50 ℃.
Due to the lower impregnation temperature, the swelling effect of the wood fiber raw material is not good, the subsequent acetylation degree is not favorably improved, and impurities in the raw material are difficult to dissolve out.
Example 12
This example provides a process for the preparation of acetylated wood fibres, identical to example 1 except that the impregnation temperature in step (1) is 170 ℃.
Too high an impregnation temperature easily causes decomposition and deterioration of the cellulose, thereby reducing the fiber strength.
Example 13
This example provides a process for the preparation of acetylated wood fibres, substantially as described in example 1, except that in step (2) the acetylation temperature is 160 ℃.
Since the temperature of the acetylation reaction is too high, the cellulose is likely to undergo side reactions such as dehydration, condensation, and oxidation, thereby reducing the degree of substitution by acetylation.
Example 14
This example provides a process for the preparation of acetylated wood fibres, substantially as described in example 1, except that the acetylation temperature in step (2) is 50 ℃.
The acetylation reaction is incomplete due to the low temperature of the acetylation reaction, so that the acetylation substitution degree is reduced.
The acetyl substitution degree in examples 1 to 14, which is the degree of esterification according to the present invention, means the number of hydroxyl groups reacted with acid per cellulose glucoside unit on average, was measured. There are 3 hydroxyl groups per glucoside unit, so the maximum theoretical degree of substitution of acetyl groups is 3.
The acetyl substitution degree is measured by adopting an alcohol soap method, and the method comprises the following specific steps:
0.2g of acetylated wood fiber and 40mL of sodium hydroxide ethanol solution are weighed and placed in a round bottom flask provided with a reflux condensing device, reflux reaction is carried out for 2 hours in an oil bath at the temperature of 90 ℃, 2-3 drops of phenolphthalein indicator are added dropwise after the solution is cooled, and finally titration is carried out with hydrochloric acid (each sample is titrated for 2 times, and the average value is taken).
The calculation formula is as follows:
in the formula, N is the bonding amount (mol); m is the mass (g) of cellulose acetate; v1 is the volume of hydrochloric acid (mL) consumed for titration of 40mL of NaOH solution; v2 is the volume (mL) of hydrochloric acid consumed for titration of the saponified cellulose acetate ethanol solution; c hydrochloric acid is the concentration (mol. L) of hydrochloric acid-1) (ii) a M is the relative molecular mass of glacial acetic acid.
TABLE 1
| Degree of substitution by acetyl group | |
| Example 1 | 0.78 |
| Example 2 | 0.72 |
| Example 3 | 0.67 |
| Example 4 | 0.62 |
| Example 5 | 0.68 |
| Example 6 | 0.80 |
| Example 7 | 0.75 |
| Example 8 | 0.71 |
| Example 9 | 0.66 |
| Example 10 | 0.72 |
| Example 11 | 0.60 |
| Example 12 | 0.43 |
| Example 13 | 0.36 |
| Example 14 | 0.32 |
In conclusion, the preparation method of the acetylated wood fiber provided by the invention can improve the acetyl content in the wood fiber, so that the acetyl substitution degree reaches 0.8, and the subsequent utilization of the acetylated wood fiber is facilitated. The wood fiber raw material can be swelled through carbonate impregnation, glacial acetic acid is easier to permeate in the subsequent acetylation process, acetylation effect is better, and silicon in the raw material can be dissolved out through carbonate solution preimpregnation; the cooking liquor and the fiber pickling liquor which are filtered and separated after cooking can recover the organic acid in the cooking liquor, so that the organic acid can be reused in acetylation, cooking and fiber washing, and the utilization rate of reagents is improved.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of acetylated wood fibers is characterized by comprising the following steps:
(1) impregnating the wood fiber raw material with an alkaline salt solution, and washing the solid after solid-liquid separation to obtain an impregnation solution and an impregnation material;
(2) mixing glacial acetic acid solution with the impregnating material obtained in the step (1), and carrying out acetylation reaction under the action of a molecular sieve solid acid catalyst to obtain acetylated wood fibers.
2. The method according to claim 1, wherein the alkaline salt solution of step (1) comprises any one of a carbonate solution, an acetate solution, or a sulfite solution or a combination of at least two thereof;
preferably, the carbonate solution comprises a sodium carbonate solution and/or a potassium carbonate solution;
preferably, the acetate solution comprises a sodium acetate solution and/or a potassium acetate solution;
preferably, the sulfite solution comprises a sodium sulfite solution and/or a potassium sulfite solution;
preferably, the mass concentration of the alkaline salt solution in step (1) is 5-50 wt%, preferably 15-30 wt%.
3. The production method according to claim 1 or 2, wherein the lignocellulosic raw material of step (1) comprises woody biomass and/or graminaceous biomass;
preferably, the woody biomass comprises any one of hardwood, softwood, or shrub, or a combination of at least two thereof;
preferably, the graminaceous biomass comprises any one or a combination of at least two of bagasse, bamboo, straw, wheat straw, corn stover, or reed.
4. The method according to any one of claims 1 to 3, wherein the mass ratio of the alkaline salt solution to the lignocellulosic feedstock in step (1) is (2-15: 1, preferably (8-12: 1;
preferably, the temperature of the impregnation in step (1) is 60-150 ℃, preferably 70-100 ℃;
preferably, the pressure of the impregnation in the step (1) is 0.1-0.2MPa, preferably 0.12-0.18 MPa;
preferably, the impregnation of step (1) is carried out for a period of 1 to 5 hours, preferably 2 to 3 hours.
5. The production method according to any one of claims 1 to 4, wherein the washing in step (1) is washing with water;
preferably, the mass ratio of the washing water amount to the solid after solid-liquid separation is (2-10) to 1, preferably (4-6) to 1;
preferably, the number of washing in step (1) is 3 to 20, preferably 5 to 8.
6. The method according to any one of claims 1 to 5, wherein the mass ratio of the wood fiber raw material in the step (1) to the glacial acetic acid solution in the step (2) is 1 (2-20), preferably 1 (8-12);
preferably, the carrier of the molecular sieve solid acid catalyst in the step (2) is titanium dioxide;
preferably, the temperature of the acetylation reaction in the step (2) is 60-150 ℃, preferably 80-120 ℃;
preferably, the acetylation reaction time in step (2) is 1-10h, preferably 2-4 h.
7. The method of any one of claims 1-6, further comprising the step of pretreating the lignocellulosic feedstock of step (1): cutting and crushing the wood fiber raw material to ensure that the length of the wood fiber raw material is less than or equal to 5cm, the width of the wood fiber raw material is less than or equal to 5cm and the thickness of the wood fiber raw material is less than or equal to 2 cm.
8. The method according to any one of claims 1 to 7, wherein the method further comprises a step of post-treating the acetylated wood fibers obtained in step (2): cooking the acetylated wood fibers obtained in the step (2) by using organic acid, and washing after solid-liquid separation;
preferably, the organic acid comprises any one of propionic acid, n-butyric acid or isobutyric acid or a combination of at least two thereof, preferably a combination of n-butyric acid and isobutyric acid;
preferably, the mass ratio of the adding amount of the organic acid to the glacial acetic acid solution in the step (2) is 1 (5-20), preferably 1 (8-12);
preferably, the cooking temperature is 100-200 ℃, preferably 140-160 ℃;
preferably, the cooking pressure is 0.1-0.2MPa, preferably 0.12-0.16 MPa;
preferably, the cooking time is 2-10h, preferably 4-6 h.
9. The method according to claim 8, wherein the washing is washing with glacial acetic acid and then with water;
preferably, the mass ratio of the glacial acetic acid used for the glacial acetic acid washing to the solid after solid-liquid separation is (2-10):1, preferably (4-6): 1;
preferably, the number of the glacial acetic acid washes is 3-20, preferably 4-8;
preferably, the mass ratio of the water used for water washing to the solid after solid-liquid separation is (2-10):1, preferably (4-6): 1;
preferably, the number of times of water washing is 3 to 20 times, preferably 4 to 8 times.
10. The production method according to any one of claims 1 to 9, characterized by comprising the steps of:
(1) soaking the cut and crushed wood fiber raw material for 1-5h at 60-150 ℃ and 0.1-0.2MPa by using an alkaline salt solution with the mass concentration of 5-50 wt%, wherein the mass ratio of the alkaline salt solution to the wood fiber raw material is (2-15):1, and washing the solid after solid-liquid separation to obtain a soaking solution and a soaking material;
(2) mixing a glacial acetic acid solution with the impregnating material obtained in the step (1), wherein the mass ratio of the wood fiber raw material in the step (1) to the glacial acetic acid solution in the step (2) is 1 (2-20), and performing acetylation reaction under the action of a titanium dioxide molecular sieve solid acid catalyst, wherein the temperature of the acetylation reaction is 60-150 ℃ and the time is 1-10h to obtain acetylated wood fibers;
(3) cooking the acetylated wood fiber obtained in the step (2) for 2-10h at 100-200 ℃ and 0.1-0.2MPa by using organic acid, wherein the mass ratio of the addition amount of the organic acid to the glacial acetic acid solution in the step (2) is 1 (5-20); after solid-liquid separation, the solid-liquid separation is washed by glacial acetic acid and then by water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010103658.0A CN111171337A (en) | 2020-02-20 | 2020-02-20 | Preparation method of acetylated lignocellulose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010103658.0A CN111171337A (en) | 2020-02-20 | 2020-02-20 | Preparation method of acetylated lignocellulose |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111171337A true CN111171337A (en) | 2020-05-19 |
Family
ID=70646947
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010103658.0A Pending CN111171337A (en) | 2020-02-20 | 2020-02-20 | Preparation method of acetylated lignocellulose |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111171337A (en) |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1082054A (en) * | 1993-07-18 | 1994-02-16 | 中国科学院广州化学研究所 | The preparation method of cellulose acetate |
| CN101062956A (en) * | 2006-04-25 | 2007-10-31 | 株式会社Itef | Method of manufacturing cellulose acetate, high temperature steam reactor vessel used in the same method, and superheated steam generator used in the same method |
| CN101139400A (en) * | 2006-09-08 | 2008-03-12 | 中国科学院过程工程研究所 | method for separating straw acetylized component and preparing straw cellulose acetate |
| CN101407550A (en) * | 2008-11-07 | 2009-04-15 | 南通醋酸纤维有限公司 | Cellulose acetate made from raw material hemp dissolving pulp, preparation and use thereof |
| CN102391378A (en) * | 2011-09-01 | 2012-03-28 | 广东上九生物降解塑料有限公司 | Method for preparing cellulose acetate from wheat straws |
| CN102802894A (en) * | 2009-06-25 | 2012-11-28 | 伊士曼化工公司 | Esterified lignocellulosic materials and methods for making them |
| WO2012168446A1 (en) * | 2011-06-10 | 2012-12-13 | Titan Wood Ltd. | Wood fibre acetylation |
| CN103874712A (en) * | 2011-10-14 | 2014-06-18 | 塞拉尼斯醋酸纤维有限公司 | Methods for synthesizing acylated cellulose through instillation of an acidic catalyst |
| CN105239435A (en) * | 2015-09-02 | 2016-01-13 | 广州市楹晟生物科技有限公司 | Treatment method of wood fiber raw material |
| CN107000242A (en) * | 2014-05-21 | 2017-08-01 | 泰坦木业有限公司 | Make the method for wood acetylation in the presence of acetylation catalyst |
| CN108383915A (en) * | 2018-01-25 | 2018-08-10 | 南通醋酸纤维有限公司 | A method of preparing acetyl cellulose |
| CN109513434A (en) * | 2018-11-26 | 2019-03-26 | 广州楹鼎生物科技有限公司 | A kind of preparation method and application of titanium dioxide solids acid catalyst |
| CN109535443A (en) * | 2018-12-27 | 2019-03-29 | 浙江大学常州工业技术研究院 | The method for hydrolysis of lignocellulosic |
| CN110407946A (en) * | 2019-08-08 | 2019-11-05 | 山东泰和水处理科技股份有限公司 | A kind of method that carried superstrong solid acid catalysis prepares Triafol T |
-
2020
- 2020-02-20 CN CN202010103658.0A patent/CN111171337A/en active Pending
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1082054A (en) * | 1993-07-18 | 1994-02-16 | 中国科学院广州化学研究所 | The preparation method of cellulose acetate |
| CN101062956A (en) * | 2006-04-25 | 2007-10-31 | 株式会社Itef | Method of manufacturing cellulose acetate, high temperature steam reactor vessel used in the same method, and superheated steam generator used in the same method |
| CN101139400A (en) * | 2006-09-08 | 2008-03-12 | 中国科学院过程工程研究所 | method for separating straw acetylized component and preparing straw cellulose acetate |
| CN101407550A (en) * | 2008-11-07 | 2009-04-15 | 南通醋酸纤维有限公司 | Cellulose acetate made from raw material hemp dissolving pulp, preparation and use thereof |
| CN102802894A (en) * | 2009-06-25 | 2012-11-28 | 伊士曼化工公司 | Esterified lignocellulosic materials and methods for making them |
| WO2012168446A1 (en) * | 2011-06-10 | 2012-12-13 | Titan Wood Ltd. | Wood fibre acetylation |
| CN102391378A (en) * | 2011-09-01 | 2012-03-28 | 广东上九生物降解塑料有限公司 | Method for preparing cellulose acetate from wheat straws |
| CN103874712A (en) * | 2011-10-14 | 2014-06-18 | 塞拉尼斯醋酸纤维有限公司 | Methods for synthesizing acylated cellulose through instillation of an acidic catalyst |
| CN107000242A (en) * | 2014-05-21 | 2017-08-01 | 泰坦木业有限公司 | Make the method for wood acetylation in the presence of acetylation catalyst |
| CN105239435A (en) * | 2015-09-02 | 2016-01-13 | 广州市楹晟生物科技有限公司 | Treatment method of wood fiber raw material |
| CN108383915A (en) * | 2018-01-25 | 2018-08-10 | 南通醋酸纤维有限公司 | A method of preparing acetyl cellulose |
| CN109513434A (en) * | 2018-11-26 | 2019-03-26 | 广州楹鼎生物科技有限公司 | A kind of preparation method and application of titanium dioxide solids acid catalyst |
| CN109535443A (en) * | 2018-12-27 | 2019-03-29 | 浙江大学常州工业技术研究院 | The method for hydrolysis of lignocellulosic |
| CN110407946A (en) * | 2019-08-08 | 2019-11-05 | 山东泰和水处理科技股份有限公司 | A kind of method that carried superstrong solid acid catalysis prepares Triafol T |
Non-Patent Citations (7)
| Title |
|---|
| LAKHYA JYOTI KONWAR 等: "Sulfonated carbon as a new, reusable heterogeneous catalyst for one-pot synthesis of acetone soluble cellulose acetate", 《RSC ADVANCES》 * |
| LIFENG YAN 等: "Solvent-free Synthesis of Cellulose Acetate by Solid Superacid Catalysis", 《JOURNAL OF POLYMER RESEARCH》 * |
| YIXIN LENG 等: "Catalytic Conversion of Cellulose to Cellulose Acetate Propionate (CAP)Over SO4", 《BULL. KOREAN CHEM. SOC》 * |
| 任冀澧 等: "《染整材料化学》", 31 July 2002, 高等教育出版社 * |
| 何小维 等: "《医用碳水化合物》", 31 January 2016, 中国轻工业出版社 * |
| 佘洁 等: "乙酸活化对固体酸与液体酸催化合成醋酸纤维素反应机制的影响研究", 《中国化学会第一届全国纤维素学术研讨会论文集》 * |
| 冷一欣 等: "SO42-/ZrO2-MgO固体酸催化剂的合成及其催化合成醋酸丙酸纤维素", 《精细化工》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bajpai et al. | Pretreatment of lignocellulosic biomass | |
| Jeihanipour et al. | Enhancement of ethanol and biogas production from high‐crystalline cellulose by different modes of NMO pretreatment | |
| Sannigrahi et al. | Fundamentals of biomass pretreatment by fractionation | |
| CN107337774B (en) | A kind of preparation method of furfural modified lignin resin base phenolic resin adhesive | |
| CN107445925B (en) | Method for preparing furan compound and liquid cycloparaffin by fully utilizing primary biomass | |
| Kim | Sequential hydrolysis of hemicellulose and lignin in lignocellulosic biomass by two-stage percolation process using dilute sulfuric acid and ammonium hydroxide | |
| CN111979819B (en) | Method for separating lignocellulosic biomass components | |
| CN102604121A (en) | Method for preparing high-quality lignin by coupling hydrothermal pretreatment and high-boiling-point alcohol | |
| JP2012102297A (en) | Method for solubilizing lignin | |
| CN103966367B (en) | Process for the preparation of saccharides | |
| CN108097312A (en) | A kind of preparation method and applications of lignocellulosic based solid acid catalyst | |
| CN108855135A (en) | A kind of carbon-based solid acid catalyst and its application in lignocellulosic depolymerization | |
| CN109826044A (en) | The separation method of cellulose, hemicellulose, lignin in cotton stalk | |
| Zhan et al. | Enhancing the potential production of bioethanol with bamboo by γ-valerolactone/water pretreatment | |
| CN111943917A (en) | Method for efficiently preparing 5-hydroxymethylfurfural by pretreating lignocellulose with formic acid | |
| KR101037708B1 (en) | Process for the pre-treatment of lignocellulosic biomass by popping method combined with microwave and process for the production of saccarification and bio-ethanol using the same | |
| Duan et al. | Acidic deep eutectic solvent treatment for viscosity control and reactivity enhancement of bamboo dissolving pulp | |
| CN105695536B (en) | Pretreatment method capable of realizing efficient enzymatic saccharification of broadleaf wood brushwood | |
| CN102409113B (en) | Method for improving cellulose hydrolysis efficiency | |
| CN111171337A (en) | Preparation method of acetylated lignocellulose | |
| WO2018133619A1 (en) | Method for producing sugar by hydrolyzing thick mash of agricultural and forest biomass raw material | |
| CN103266148B (en) | Preprocessing method capable of effectively improving efficiency of generating fermentable sugar by bamboo cellulose enzyme hydrolysis | |
| CN114573529A (en) | Method for continuously and efficiently catalyzing poplar to convert furfural | |
| CN102675086B (en) | Method for preparing levulinic acid from steam explosion produced straw short fiber by adding polymerization inhibitor and performing solid acid catalysis | |
| CN111535068A (en) | Method for extracting bagasse fibers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200519 |