CN111101394B - Method for separating cellulose from wood fiber raw material by one-step method - Google Patents
Method for separating cellulose from wood fiber raw material by one-step method Download PDFInfo
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- CN111101394B CN111101394B CN202010065800.7A CN202010065800A CN111101394B CN 111101394 B CN111101394 B CN 111101394B CN 202010065800 A CN202010065800 A CN 202010065800A CN 111101394 B CN111101394 B CN 111101394B
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Abstract
The invention discloses a method for separating cellulose from a wood fiber raw material by a one-step method, which comprises the following steps: (1) mechanically pulverizing the collected lignocellulosic feedstock into particles; (2) putting the raw materials in the step (1) into a reactor, and adding a mixed aqueous solution of peroxyacetic acid and maleic acid according to a certain solid-to-liquid ratio; (3) setting the reaction time and temperature of the container to carry out reaction; (4) after the reaction is finished, cellulose solid is obtained by separation, and the obtained filtrate is recovered. The method can remove lignin and hemicellulose in one step, and has the advantages of simple separation process, low production cost, mild reaction conditions, short time consumption and wide raw material applicability. Therefore, the method has strong practicability and is easy to popularize and industrialize.
Description
Technical Field
The invention relates to a method for separating cellulose from a wood fiber raw material in one step, belonging to a chemical pretreatment method of the wood fiber raw material.
Background
Lignocellulosic biomass is produced by plant photosynthesis, and is a renewable resource with abundant content and low cost. The yield of the lignocellulosic biomass produced by annual photosynthesis on the earth reaches 1 multiplied by 1012Ton, about 20 times of world energy consumption. The conversion of lignocellulosic biomass into biofuels or biobased materials will reduce the social dependence on non-renewable resources such as petroleum, and at the same time reduce the net emission of greenhouse gases. The main components of the lignocellulosic biomass are cellulose, hemicellulose and lignin, wherein the cellulose accounts for 30-35% of the dry weight of the lignocellulosic biomass, and is a polysaccharide which is widely distributed and has the largest content in nature. Cellulose, as a raw material that is abundant in resources, low in price, and not fully utilized, can be applied to paper making, chemicals, and other industrial products. However, in lignocellulosic biomass cellulose is tightly encapsulated by lignin and hemicellulose together, forming a dense network structure. The net structure restricts the woodComprehensive utilization of the biomass of the cellulose. Physical, chemical and biological pretreatment methods are generally required to break the network structure in the lignocellulosic biomass, so as to achieve the purpose of removing lignin and hemicellulose barriers and enriching cellulose components.
Chinese patent CN 102212582A discloses a method for preparing cellulose from straws by a biological method, which comprises the steps of pretreating straws by using a composite biocatalyst consisting of laccase, catalase and hydrogen peroxide, and obtaining the cellulose with the purity of 99% under the conditions that the reaction temperature is 60-80 ℃ and the reaction time is 1-3 h. The method has the advantages of small environmental pollution, cleanness and the like, but has large enzyme quantity, high cost and long reaction time.
Chinese patent CN 102251424A discloses a method for extracting cellulose in one step, which comprises the steps of dispersing plant straws in a mixed solution of organic solvents (acetone, methanol, toluene and ethanol) and water, adding inorganic alkali and an oxidant, and reacting for 10-40min under the conditions that the pressure is 1-5MPa and the temperature is 80-150 ℃, wherein the solid yield is 44%. The method has simple production process and high efficiency, but the toxic organic solvent used in the production process causes harm to the environment, and the method has high reaction pressure, harsh conditions and high requirements on equipment, and is not beneficial to actual production.
Chinese patent CN 102995475A discloses a method for extracting cellulose from bagasse, which comprises using bagasse as a raw material, primarily delignifying with sodium hydroxide/oxygen, deeply delignifying with sodium hydroxide/hydrogen peroxide/cobalt acetate, and finally removing hemicellulose with potassium hydroxide to obtain the cellulose from the bagasse. The method has mild reaction conditions, the purity of the product cellulose is 99.9 percent, but the process is complicated, the production investment is high, and the method is not beneficial to large-scale production.
Chinese patent CN 105507051A discloses a method for efficiently separating wood fiber raw material, which comprises the steps of taking wood fiber biomass as raw material, adding 70-90% formic acid aqueous solution and 0.2-10 wt% oxidant (hydrogen peroxide, peracetic acid, green oxygen, potassium permanganate) into the wood fiber biomass, reacting for 10min-3h at the temperature of 105-. The process has mild conditions, is easy to operate, can improve the utilization rate of each component, but has strong corrosivity of high-concentration formic acid, is easy to damage equipment and is not beneficial to industrial application, and meanwhile, the steam formed by the formic acid is mixed with air and is easy to explode under the condition of high temperature, so that potential safety hazards exist.
Therefore, the development of a cellulose separation method with simple treatment process, environmental protection, low production cost and wide raw material applicability is very important for resource utilization of the wood fiber biomass.
Disclosure of Invention
The invention aims to provide a method for separating cellulose from a wood fiber biomass raw material by a one-step method, which has the advantages of high efficiency, mild reaction conditions, environmental friendliness, wide raw material applicability, simple extraction process and the like.
The cellulose separation method provided by the invention comprises the following steps:
(1) the collected lignocellulosic feedstock is mechanically comminuted into particles.
(2) Putting the raw materials in the step (1) into a reactor, and adding a mixed aqueous solution of peroxyacetic acid and maleic acid according to a certain solid-to-liquid ratio.
(3) Setting the reaction time and temperature of the container to perform the reaction.
(4) After the reaction is finished, cellulose solid is obtained by separation, and the obtained filtrate is recovered.
In a specific case, the wood fiber raw material in the step (1) may be at least one of corn straw, wheat straw, rice straw, birch, and poplar. After crushing, the mixture is sieved by a 40-mesh sieve, thereby facilitating the subsequent reaction.
Preferably, in the mixed aqueous solution in the step (2), the concentration of the peroxyacetic acid is 0.5 wt% to 2.5 wt%, the concentration of the maleic acid is 1 wt% to 5 wt%, and the solid-to-liquid ratio (wt/vol) is 1:10 to 1:40 (the ratio of the mass of the solid wood fiber raw material to the volume of the mixed aqueous solution). .
Preferably, the reaction temperature in the step (3) is 100-. The reaction is preferably carried out in a closed reaction vessel.
The invention has the beneficial effects that:
in the invention, the peroxyacetic acid and the maleic acid are used for pretreating the wood fiber raw material to separate the cellulose. Compared with the traditional inorganic acid (sulfuric acid), the maleic acid has the advantages of weak acidity, greenness, reproducibility and the like, has good catalytic activity on hemicellulose, is high in selectivity when degrading the hemicellulose, can prevent glucose and xylose from being further degraded into inhibitors such as furfural and the like, and is beneficial to recycling products such as xylose in subsequent filtrate. The peroxyacetic acid is used as an oxidant, so that the lignin in the wood fiber raw material can be effectively removed, the bleaching effect can be achieved, and the quality of the cellulose is improved. The concentration of the peroxyacetic acid and the maleic acid used in the method is low, no environmental pollution is caused, the use of high-concentration acid and alkali in the traditional cellulose separation method is avoided, and the method has the characteristic of environmental friendliness. The method can remove lignin and hemicellulose in one step, and has the advantages of simple separation process, low production cost, mild reaction conditions, short time consumption and wide raw material applicability. Therefore, the method has strong practicability and is easy to popularize and industrialize.
Drawings
FIG. 1 is a Fourier transform infrared spectrum of the product obtained in example 1 of the present invention.
FIG. 2 is a scanning electron micrograph of the product obtained in example 1.
Detailed Description
The invention will be further elucidated below in connection with crop stalks, poplar and birch as starting materials, said test methods being, without particular mention, conventional methods in which the cellulose, hemicellulose and lignin contents are determined according to the method described in NREL/TP-510-.
Example 1
Adding 4g of corn straw, 160 mL1.5wt% of peroxyacetic acid and 3 wt% of maleic acid mixed aqueous solution into a reaction container, setting the reaction temperature of the container to be 130 ℃ and keeping for 60min, after the reaction is finished, cooling to room temperature and filtering to obtain solid, namely corn cellulose, wherein the cellulose yield is 85%, the lignin removal rate is 91% and the hemicellulose removal rate is 90%.
As shown in fig. 1, the corn cellulose obtained in example 1 showed characteristic absorption peaks of cellulose: 898cm-1、1057cm-1、1109cm-1、1600cm-1And lignin characteristic peak: 1515cm-1、1606cm-1、833cm-1And hemicellulose characteristic peaks: 1248cm-1None are present. The method removes most of lignin and hemicellulose, and the obtained cellulose solid has higher purity. As can be seen from FIG. 2, the obtained cellulose is in the form of fiber bundles, and the surface is smooth and fluffy, which shows that the method can remove lignin and hemicellulose.
Example 2
Adding 8g of corn straw, 160mL of mixed aqueous solution of 1.5 wt% of peroxyacetic acid and 3 wt% of maleic acid into a reaction container, setting the reaction temperature of the container to be 130 ℃ and keeping for 60min, cooling to room temperature after the reaction is finished, and filtering to obtain solid, namely corn cellulose, wherein the cellulose yield is 87%, the lignin removal rate is 88%, and the hemicellulose removal rate is 88%.
Example 3
Adding 16g of corn straw, 160mL of mixed aqueous solution of 1.5 wt% of peroxyacetic acid and 3 wt% of maleic acid into a reaction container, setting the reaction temperature of the container to be 130 ℃ and keeping for 60min, cooling to room temperature after the reaction is finished, and filtering to obtain solid, namely corn cellulose, wherein the cellulose yield is 86%, the lignin removal rate is 76%, and the hemicellulose removal rate is 86%.
Example 4
Adding 4g of corn straw, 160 mL1.5wt% of peroxyacetic acid and 5 wt% of maleic acid mixed aqueous solution into a reaction container, setting the reaction temperature of the container as 100 ℃ and keeping for 30min, after the reaction is finished, cooling to room temperature and filtering to obtain solid, namely corn cellulose, wherein the cellulose yield is 86%, the lignin removal rate is 69% and the hemicellulose removal rate is 58%.
Example 5
Adding 4g of corn straw, 160mL of mixed aqueous solution of 1.5 wt% of peroxyacetic acid and 3 wt% of maleic acid into a reaction container, setting the reaction temperature of the container to be 140 ℃ and keeping for 30min, cooling to room temperature after the reaction is finished, and filtering to obtain solid, namely corn cellulose, wherein the cellulose yield is 80%, the lignin removal rate is 91%, and the hemicellulose removal rate is 93%.
Example 6
Adding 4g of corn straw, 160mL of a mixed aqueous solution of 0.5 wt% of peroxyacetic acid and 3 wt% of maleic acid into a reaction container, setting the reaction temperature of the container to be 130 ℃ and keeping for 30min, cooling to room temperature after the reaction is finished, and filtering to obtain a solid, namely corn cellulose, wherein the cellulose yield is 87%, the lignin removal rate is 65%, and the hemicellulose removal rate is 85%.
Example 7
Adding 4g of corn straw, 160mL of mixed aqueous solution of 1.5 wt% of peroxyacetic acid and 5 wt% of maleic acid into a reaction container, setting the reaction temperature of the container to be 130 ℃ and keeping for 30min, cooling to room temperature after the reaction is finished, and filtering to obtain solid, namely corn cellulose, wherein the cellulose yield is 86%, the lignin removal rate is 92% and the hemicellulose removal rate is 86%.
Example 8
Adding 4g of wheat straw, 160mL of mixed aqueous solution of 1.5 wt% of peroxyacetic acid and 3 wt% of maleic acid into a reaction container, setting the reaction temperature of the container to be 130 ℃ and keeping the temperature for 90min, cooling to room temperature after the reaction is finished, and filtering to obtain solid, namely wheat cellulose, wherein the cellulose yield is 83%, the lignin removal rate is 86% and the hemicellulose removal rate is 92%.
Example 9
Adding 4g of rice straw, 160mL of mixed aqueous solution of 1.5 wt% of peroxyacetic acid and 3 wt% of maleic acid into a reaction container, setting the reaction temperature of the container to be 130 ℃ and keeping for 60min, cooling to room temperature after the reaction is finished, and filtering to obtain solid, namely rice cellulose, wherein the cellulose yield is 76%, the lignin removal rate is 82%, and the hemicellulose removal rate is 93%.
Example 10
Adding 4g of birch wood powder, 160mL of mixed aqueous solution of 1.5 wt% of peroxyacetic acid and 3 wt% of maleic acid into a reaction container, setting the reaction temperature of the container to be 130 ℃ and keeping the temperature for 90min, cooling to room temperature after the reaction is finished, and filtering to obtain solid birch cellulose, wherein the cellulose yield is 94%, the lignin removal rate is 94%, and the hemicellulose removal rate is 86%.
Example 11
Adding 4g of poplar powder, 160mL of a mixed aqueous solution of 1.5 wt% of peroxyacetic acid and 3 wt% of maleic acid into a reaction vessel, setting the reaction temperature of the vessel to be 130 ℃ and keeping the reaction temperature for 90min, cooling to room temperature after the reaction is finished, and filtering to obtain solid poplar cellulose, wherein the cellulose yield is 94%, the lignin removal rate is 95%, and the hemicellulose removal rate is 87%.
Claims (2)
1. A one-step process for separating cellulose from a lignocellulosic feedstock comprising the steps of:
(1) mechanically pulverizing the collected lignocellulosic feedstock into particles;
(2) putting the raw materials in the step (1) into a reactor, and adding a mixed aqueous solution of peroxyacetic acid and maleic acid according to a certain solid-to-liquid ratio; in the mixed aqueous solution, the concentration of the peroxyacetic acid is 0.5-2.5 wt%, the concentration of the maleic acid is 1-5 wt%, and the solid-to-liquid ratio (wt/vol) is 1:10-1: 40;
(3) setting the reaction temperature of the container at 100-140 ℃ and the reaction time at 10-90min for reaction;
(4) after the reaction is finished, cellulose solid is obtained by separation, and the obtained filtrate is recovered.
2. The method according to claim 1, wherein the lignocellulosic raw material in step (1) is at least one of corn stover, wheat straw, rice straw, birch, and poplar.
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| CN113083039A (en) * | 2021-04-15 | 2021-07-09 | 中国农业大学 | Method for green and efficient preparation of corn straw-based cellulose triacetate porous membrane |
| CN114182554B (en) * | 2021-12-17 | 2023-05-05 | 大连工业大学 | Method for pretreating lignocellulose biomass and separating lignin |
| CN116787566B (en) * | 2023-07-24 | 2024-03-08 | 南京林业大学 | Sulfonated straw flame retardant, and preparation method and application thereof |
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| CN102604120A (en) * | 2012-02-29 | 2012-07-25 | 福州大学 | Method for preparing lignin sulfonate dispersing agent by using two-step oxidization method |
| CN103924468A (en) * | 2014-05-16 | 2014-07-16 | 长春工业大学 | Separation method of lignocellulose raw material ingredients |
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| WO2004012510A1 (en) * | 2002-08-06 | 2004-02-12 | Ecolab Inc. | Critical fluid antimicrobial compositions and their use and generation |
| CN102604120A (en) * | 2012-02-29 | 2012-07-25 | 福州大学 | Method for preparing lignin sulfonate dispersing agent by using two-step oxidization method |
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