CN113564955B - Method for treating plant fiber raw material by acetic acid solution - Google Patents

Method for treating plant fiber raw material by acetic acid solution Download PDF

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Publication number
CN113564955B
CN113564955B CN202010351029.XA CN202010351029A CN113564955B CN 113564955 B CN113564955 B CN 113564955B CN 202010351029 A CN202010351029 A CN 202010351029A CN 113564955 B CN113564955 B CN 113564955B
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acetic acid
plant fiber
fiber raw
raw material
cooking
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CN113564955A (en
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张睿哲
刘运思
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Guangzhou Yuding Biotechnology Co ltd
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Guangzhou Yuding Biotechnology Co ltd
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/003—Pulping cellulose-containing materials with organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
    • C07G1/00—Lignin; Lignin derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K1/00—Glucose; Glucose-containing syrups
    • C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/22—Other features of pulping processes
    • D21C3/26—Multistage processes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/02—Chemical or chemomechanical or chemothermomechanical pulp
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/12—Pulp from non-woody plants or crops, e.g. cotton, flax, straw, bagasse
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Abstract

The invention relates to a method for treating plant fiber raw materials by acetic acid solution, which comprises the following steps: performing primary cooking on the plant fiber raw material by using acetic acid solution, and performing solid-liquid separation after the cooking is finished to obtain cooking liquid and primary-cooked plant fiber raw material; performing secondary steaming on the plant fiber raw material steamed for the first time by using acetic acid solution, and performing solid-liquid separation after steaming is finished to obtain steaming liquid and the plant fiber raw material steamed for the second time; washing the second steamed plant fiber raw material to obtain a washing liquid and a treated plant fiber raw material; the obtained cooking liquid and washing liquid are recycled. The method uses the high-concentration acetic acid solution to treat the plant fiber raw material, does not need to additionally add a catalyst, reduces the types and the use amount of solvents, has high extraction rate of three components of the raw material, improves the utilization rate of the raw material, and increases the treatment benefit.

Description

Method for treating plant fiber raw material by acetic acid solution
Technical Field
The invention belongs to the technical field of biomass chemical industry, relates to a treatment method of plant fiber raw materials, and particularly relates to a method for treating plant fiber raw materials by an acetic acid solution.
Background
The most part of the agricultural and forestry wastes such as rich straw in China are directly burned at present, so that precious biomass resources are wasted, and serious environmental pollution is caused. The use of these inexpensive lignocellulose resources to produce fermentable sugars, which in turn are converted into bio-based chemicals, bioenergy and bio-based materials required by humans, is an important content for biomass conversion and development of bioeconomical, and has important strategic significance for sustainable development of socioeconomic.
The plant fiber raw material is rich in cellulose, hemicellulose and lignin components, and the three components form a supermolecular compound with compact structure in a physical or chemical combination mode, so that the supermolecular compound has stronger hydrolysis resistance. In order to increase the saccharification rate of the plant fiber raw material, the lignocellulose needs to be pretreated. Currently, the pretreatment methods mainly include physical methods, physicochemical methods, chemical methods and biological methods.
The physical method mainly reduces the crystallinity of cellulose by means of mechanical crushing, radiation and the like, increases the surface area of lignocellulose, has high energy consumption and poor industrial adaptability. The physicochemical method mainly comprises a hydrothermal method and a steam explosion method, and the enzyme hydrolysis process is promoted by removing most hemicellulose through dissolution, chemicals are not required to be added in the hydrothermal method, so that the wastewater is easy to treat, but the pretreatment strength is low, and the pretreatment effect is poor; the steam explosion method has simple process, high requirement on acid-coated steam explosion equipment and high equipment investment cost. The biological method is used for removing lignin by utilizing microorganisms, and has the advantages of no pollution, mild treatment conditions, long treatment period and low saccharification rate of cellulose after pretreatment. The chemical method comprises an acid and alkali pretreatment method, wherein the acid pretreatment generally adopts common strong inorganic acid, is easy to generate a large amount of inhibitors, has strong corrosiveness and has high requirements on equipment; the alkali pretreatment method can effectively dissolve hemicellulose and lignin, but the wastewater treatment difficulty is high.
CN 105239435A discloses a method for treating plant fiber raw materials, which comprises the following steps: (1) pre-impregnation: the plant fiber raw material is added with Na 2 CO 3 Soaking in aqueous solution; (2) steaming: and (3) taking an organic acid aqueous solution as a cooking solvent, adding inorganic acid as a catalyst, and cooking the impregnated plant fiber raw material. The method can improve the pulp yield of the paper pulp, reduce the ash content and improve the comprehensive performance of the paper pulp, but the method adds an inorganic acid catalyst.
CN 106191158A discloses a clean and safe pretreatment method of plant fiber raw materials, which comprises the following steps: (1) Taking natural lignocellulose as a raw material, crushing, and pretreating with 10-20% acetic acid (mass concentration) at 120-150 ℃ for 10-60min to effectively hydrolyze and dissolve hemicellulose; (2) Recovering acetic acid by reduced pressure evaporation to obtain pretreated materials, and analyzing the composition and the material yield; (3) Mixing the pretreated material with cellulose, adding water and pH buffer, mixing to substrate concentration of 5-20%, controlling pH at 4-6, controlling cellulose dosage at 10-40FPIU/g cellulose, and performing enzymolysis at 45-55deg.C and 100-200r/min for 48-72 hr to obtain glucose. The method uses a biological method to carry out enzymolysis on the pretreated material, has long treatment period, and can not effectively treat the wastewater generated by the plant fiber raw material.
In this regard, the method for treating the plant fiber raw material has the advantages of low water consumption, less wastewater generation, simple process and low treatment cost, is beneficial to reducing the cost of extracting cellulose, hemicellulose and lignin from the wood raw material for enterprises, improves the economic benefit of the enterprises, and can reduce environmental pollution.
Disclosure of Invention
The invention aims to provide a method for treating plant fiber raw materials by using acetic acid solution with high concentration, which is used for treating plant fiber raw materials without adding extra catalyst, reduces the types and the use amount of solvents, has high extraction rate of cellulose, lignin and sugar in the raw materials, improves the utilization rate of the raw materials, relatively reduces the quality requirements on the plant fiber raw materials, and is beneficial to improving the utilization rate of the raw materials.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the invention provides a method for treating plant fiber raw materials by acetic acid solution, which comprises the following steps:
(1) Steaming the plant fiber raw material by using acetic acid solution, and performing solid-liquid separation after steaming to obtain steaming liquid and first-time steaming plant fiber raw material; or, after the first cooking is finished, replacing the cooking liquid by using acetic acid solution;
(2) Performing second cooking on the first-time cooked plant fiber raw material by using acetic acid solution; or directly performing secondary cooking on the mixed liquor obtained after the replacement; after the second steaming is finished, carrying out solid-liquid separation to obtain steaming liquid and second steaming plant fiber raw materials;
(3) Washing the second steamed plant fiber raw material obtained in the step (2) to obtain a washing liquid and a treated plant fiber raw material;
(4) And (3) respectively and independently recycling the cooking liquid obtained in the step (1), the cooking liquid obtained in the step (2) and the washing liquid obtained in the step (3).
According to the invention, the plant fiber raw material is treated by only adopting the acetic acid solution, and the plant fiber raw material can be steamed without adding a catalyst by only controlling the steaming condition, so that the types and the addition amount of solvents used in the treatment of the plant fiber raw material are reduced, the quality requirements on the plant fiber raw material are reduced, and the treatment cost and the waste liquid treatment amount are reduced. The plant fiber raw material steamed by the acetic acid solution has good separation effect, high yields of cellulose, lignin and sugar, and improves the utilization rate of the plant fiber raw material.
The step (2) of the invention is that the acetic acid solution is used for carrying out the second cooking on the first-time cooking plant fiber raw material, namely, when the solid-liquid separation is carried out after the first cooking, the acetic acid solution is used for carrying out the second cooking after being mixed with the first-time cooking plant fiber raw material; when the acetic acid solution is used to replace the cooking liquid, the mixture of the acetic acid solution and the first-time cooked plant fiber raw material can be directly subjected to second-time cooking.
Preferably, the plant fiber raw material comprises woody biomass and/or grassy biomass.
Preferably, the woody biomass comprises any one or a combination of at least two of a hardwood, a softwood or a shrub, for example, a combination of a hardwood and a softwood, a combination of a softwood and a shrub, a combination of a hardwood and a shrub, or a combination of a hardwood, a softwood and a shrub.
Preferably, the grassy biomass comprises any one or a combination of at least two of bagasse, bamboo, straw, wheat straw, corn stover, or reed, typically but not limited to, bagasse and bamboo, bamboo and straw, straw and wheat straw, corn stover and reed, corn stover and reed, bamboo, straw and wheat straw, or bagasse, bamboo, straw, wheat straw, corn straw and reed.
Preferably, the mass concentration of the acetic acid solution in step (1) and the mass concentration of the acetic acid solution in step (2) are respectively 60-100wt%, such as 60wt%, 70wt%, 80wt%, 85wt%, 90wt%, 95wt% or 100wt%, but are not limited to the recited values, and other non-recited values in the numerical range are equally applicable, preferably 75-100wt%.
According to the invention, the plant fiber raw material is treated by selecting the acetic acid solution with high mass concentration, so that no additional catalyst is needed, and the treatment difficulty and cost of the waste liquid are reduced. The utilization rate of the acetic acid can be improved by recycling the acetic acid in the treatment liquid, and the lignin and sugar in the treatment liquid can be recycled, so that the economic benefit of enterprises is improved.
Preferably, the mass ratio of the plant fiber raw material to the acetic acid solution in the step (1) is 1 (3-15), for example, 1:3, 1:5, 1:7, 1:9, 1:11, 1:13 or 1:15, but is not limited to the recited values, and other non-recited values in the numerical range are equally applicable, preferably 1 (4-12).
Preferably, the temperature of the first cooking in step (1) is 115-180deg.C, such as 115 deg.C, 125 deg.C, 130 deg.C, 135 deg.C, 140 deg.C, 150 deg.C, 160 deg.C, 165 deg.C, 170 deg.C, 175 deg.C or 180 deg.C, but not limited to the values recited, other values not recited in the range of values are equally applicable, preferably 130-160deg.C.
Preferably, the absolute pressure of the first cooking in step (1) is 0.2-1MPa, for example, 0.2MPa, 0.3MPa, 0.5MPa, 0.7MPa or 1MPa, but not limited to the values listed, and other values not listed in the range of values are equally applicable, preferably 0.3-0.8MPa.
Preferably, the time of the first cooking in step (1) is 1-8h, for example, 1h, 2h, 3h, 4h, 5h, 6h, 6.5h, 7h, 7.5h or 8h, but not limited to the recited values, other non-recited values in the range are equally applicable, preferably 2-6h.
Preferably, the mass ratio of the plant fiber raw material to the acetic acid solution in the step (2) is 1 (3-15), for example, 1:3, 1:5, 1:7, 1:9, 1:11, 1:13 or 1:15, but is not limited to the recited values, and other non-recited values in the numerical range are equally applicable, preferably 1 (4-12).
When the cooking liquid is replaced by the acetic acid solution after the first cooking in the step (1), the acetic acid solution used for replacement is 60-100wt% of the acetic acid solution, and the mass ratio of the acetic acid solution used for replacement to the plant fiber raw material is (3-15): 1. When the acetic acid solution is used to replace the cooking liquid, the mixture of the acetic acid solution and the first-time cooked plant fiber raw material can be directly subjected to second-time cooking.
Preferably, the temperature of the second cooking in step (2) is 100-160 ℃, for example, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃ or 160 ℃, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable, preferably 120-150 ℃.
Preferably, the time of the second cooking in step (2) is 0.5-5h, for example, 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5h, but not limited to the recited values, other non-recited values in the range of values are equally applicable, preferably 2-4h.
Preferably, the absolute pressure of the cooking in the step (2) is 0.1-0.6MPa, for example, 0.1MPa, 0.2MPa, 0.3MPa, 0.35MPa, 0.4MPa, 0.45MPa, 0.5MPa or 0.6MPa, but not limited to the values listed, other non-listed values in the range of values are equally applicable, preferably 0.2-0.6MPa.
Preferably, the mass concentration of the acetic acid solution in step (3) is 70-100wt%, for example, 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, 95wt%, or 100wt%, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable, preferably 80-100wt%.
According to the invention, the plant fiber raw material is steamed by adopting the high-quality concentration acetic acid solution, the plant fiber raw material is washed by adopting the high-quality concentration acetic acid solution, the difficulty of recovery treatment of the washing liquid is reduced, the recovered acetic acid is recycled for steaming and/or washing by concentrating the washing liquid, and sugar and/or lignin remained in the concentrated liquid can be recovered, so that the economic benefit of enterprises is improved.
Preferably, the washing of step (3) is: alternately washing with acetic acid solution and water to obtain acetic acid washing solution and treated plant fiber raw material; or alternatively washing with acetic acid and acetic acid extractant, and desolventizing the washed plant fiber raw material to obtain the treated plant fiber raw material and mixed washing liquid.
The concentration of acetic acid used for washing is 70 to 100wt%, for example, 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, 95wt% or 100wt%, but not limited to the values recited, other values not recited in the numerical range are equally applicable, and preferably 80 to 100wt%.
Preferably, the acetic acid extractant includes any one or a combination of at least two of an ester acetic acid extractant, an organic phosphorus acetic acid extractant, an organic amine acetic acid extractant, or a ketone acetic acid extractant, and typical but non-limiting combinations include a combination of an ester acetic acid extractant and an organic phosphorus acetic acid extractant, a combination of an organic phosphorus acetic acid extractant and an organic amine acetic acid extractant, a combination of an organic amine acetic acid extractant and a ketone acetic acid extractant, or a combination of an ester acetic acid extractant, an organic phosphorus acetic acid extractant and an organic amine acetic acid extractant, or a combination of an ester acetic acid extractant, an organic phosphorus acetic acid extractant, an organic amine acetic acid extractant, and a ketone acetic acid extractant, and preferably an ester acetic acid extractant.
Preferably, the ester acetic acid extractant comprises any one or a combination of at least two of ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, ethyl n-valerate or glyceryl acetate, and typical but non-limiting combinations include ethyl acetate in combination with n-propyl acetate, n-propyl acetate in combination with isopropyl acetate, isopropyl acetate in combination with n-butyl acetate, n-butyl acetate in combination with isobutyl acetate, sec-butyl acetate in combination with tert-butyl acetate, tert-butyl acetate in combination with ethyl n-valerate, ethyl n-valerate in combination with glyceryl acetate.
Preferably, the number of times of the alternate washing in the step (3) is 2-10 times, for example, may be 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times or 10 times, but is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
The alternating washing is at least 1 acetic acid washing and at least 1 water or acetic acid extractant washing, wherein the 1 st washing is acetic acid washing, and the last 1 washing is water or acetic acid extractant washing. For example, when the acetic acid and water are used to wash alternately 4 times, the 1 st washing is acetic acid washing, the last 1 washing is water washing, and the two middle washing is optionally acetic acid washing and/or water washing, for example, acetic acid washing, and water washing, acetic acid washing, water washing, and water washing, acetic acid washing, water washing, and water washing, or acetic acid washing, water washing, and water washing.
When the acetic acid and the acetic acid extractant are used for washing for 4 times alternately, the 1 st washing is acetic acid washing, the last 1 washing is acetic acid extractant washing, the two middle washing is acetic acid washing and/or acetic acid extractant washing, for example, acetic acid washing and acetic acid extractant washing can be carried out, acetic acid washing, acetic acid extractant washing and acetic acid extractant washing, acetic acid washing and acetic acid extractant washing, or acetic acid washing, acetic acid extractant washing and acetic acid extractant washing.
Preferably, the desolventizing temperature is 60 to 150 ℃, and may be 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, or 150 ℃, for example, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the temperature of the concentration and recovery acetic acid treatment of the cooking solution obtained in the step (1) and the step (2) in the step (4) is 50-130 ℃ independently, for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃ or 130 ℃, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable; the vacuum degree is-0.1 MPa to 0MPa, and for example, -0.1MPa, -0.08MPa, -0.05MPa, -0.03MPa, -0.01MPa, -0.005MPa or 0MPa, but the vacuum degree is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, in the step (4), when the cooking solution obtained in the step (1) is concentrated to recover acetic acid, the concentration multiple of the cooking solution is 3-10 times, for example, 3-5 times, 7 times, 8 times, 9 times or 10 times, but the concentration multiple is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, in the step (4), when the cooking solution obtained in the step (2) is concentrated to recover acetic acid, the concentration multiple of the cooking solution is 3-10 times, for example, 3-5 times, 7 times, 8 times, 9 times or 10 times, but the concentration multiple is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, in the step (4), the acetic acid washing liquid obtained in the step (3) is recovered to concentrate the acetic acid washing liquid by 5-30 times under the conditions that the temperature is 50-130 ℃ and the vacuum degree is-0.1-0 MPa, and the acetic acid and the concentrated liquid are recovered; the temperature of the recovery treatment is 50 to 130 ℃, for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃ or 130 ℃, but the recovery treatment is not limited to the values listed, and other values not listed in the numerical range are equally applicable; the vacuum degree is-0.1 MPa to 0MPa, for example, -0.1MPa, -0.08MPa, -0.05MPa, -0.03MPa or 0MPa, but the vacuum degree is not limited to the recited values, and other non-recited values in the numerical range are equally applicable; the concentration may be 5-30 times, for example, 5-10 times, 15 times, 20 times, 25 times or 30 times, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, in the step (4), the mixed washing liquid obtained in the step (3) is recovered and separated into acetic acid and an acetic acid extractant through rectification.
The rectification method is a conventional rectification method in the field, and the invention is not repeated herein, and the acetic acid extractant in the mixed washing liquid are separated by rectification, so that the acetic acid and the acetic acid extractant can be reused for washing the plant fiber raw material steamed for the second time, thereby reducing the washing cost.
Preferably, the method further comprises separating lignin from the sugar solution from the concentrate obtained in step (4) at a temperature of 40-100deg.C, such as 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100deg.C, but not limited to the values recited, and other values not recited in the range of values are equally applicable.
The method for separating lignin from sugar solution of the concentrated solution comprises, but is not limited to, conventional dilution, and separation of lignin from sugar solution is realized by diluting the concentrated solution at 40-100 ℃.
As a preferred technical solution of the method according to the invention, the method comprises the steps of:
(1) Using 60-100wt% acetic acid solution to cook plant fiber raw material for 1-8h at 115-180 ℃ under absolute pressure of 0.2-1MPa, wherein the mass ratio of plant fiber raw material to acetic acid solution is 1 (3-15), and after the cooking is finished, carrying out solid-liquid separation to obtain cooking liquid and first-time cooking plant fiber raw material; or, after the cooking is finished, replacing the cooking liquid by using an acetic acid solution with the concentration of 60-100wt%, wherein the mass ratio of the replaced acetic acid solution to the plant fiber raw material is (3-15): 1;
(2) Using acetic acid solution with the concentration of 60-100wt% to cook the plant fiber raw material for 0.5-5h under the conditions that the temperature is 100-160 ℃ and the absolute pressure is 0.1-0.6MPa, wherein the mass ratio of the plant fiber raw material to the acetic acid solution for the first time is 1 (3-15); or directly steaming the mixed solution obtained after the replacement for 0.5-5h under the conditions that the temperature is 100-160 ℃ and the absolute pressure is 0.1-0.6 MPa; after the cooking is finished, carrying out solid-liquid separation to obtain cooking liquid and a second-time cooking plant fiber raw material;
(3) Alternately washing the plant fiber raw material obtained in the step (2) for 2-10 times by using an acetic acid solution with the concentration of 70-100wt% and water to obtain a treated plant fiber raw material and an acetic acid washing solution; or alternatively washing the plant fiber raw material obtained in the step (2) for the second time by using an acetic acid solution with the concentration of 70-100wt% and an acetic acid extractant for 2-10 times, and desolventizing the washed plant fiber raw material at 60-150 ℃ to obtain a treated plant fiber raw material and a mixed washing solution;
(4) Recovering the cooking liquid obtained in the step (1), the cooking liquid obtained in the step (2) and the washing liquid obtained in the step (3) respectively and independently, wherein the temperature for recovering the cooking liquid obtained in the step (1) and the cooking liquid obtained in the step (2) is 50-130 ℃, the vacuum degree is-0.1-0 MPa, and the multiple of concentration is 3-10 times, so as to obtain acetic acid and concentrated solution; recovering the washing liquid obtained in the step (3);
The recovery treatment comprises the steps of recovering the acetic acid washing liquid obtained in the step (3) to concentrate the acetic acid washing liquid for 5-30 times under the conditions that the temperature is 50-130 ℃ and the vacuum degree is-0.1 MPa to 0MPa, and recovering to obtain acetic acid; or, recovering the mixed washing liquid obtained in the step (3) to obtain acetic acid and an acetic acid extractant through rectification separation;
(5) And (3) separating lignin from sugar solution from the concentrated solution obtained in the step (4) at the temperature of 40-100 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the high-concentration acetic acid solution is used for treating the plant fiber raw material, so that no additional catalyst is needed, the types and the use amount of solvents are reduced, and the treatment cost and the risk of environmental pollution are reduced;
(2) According to the invention, the acetic acid solution is used for treating the plant fiber raw material, and the plant fiber raw material is concentrated, recycled and used, so that the production water is reduced, the production cost is reduced, the pollution to the environment is reduced, and the method is energy-saving and environment-friendly;
(3) According to the invention, the plant fiber raw material is treated by using the acetic acid solution, and lignin, cellulose and sugar in the plant fiber raw material can be separated without adding other auxiliary agents, so that the efficient extraction of the plant fiber raw material is realized.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a method for treating plant fiber raw materials by acetic acid solution, wherein the plant fiber raw materials are bamboo, and the method comprises the following steps:
(1) Steaming plant fiber raw materials for 4 hours at the temperature of 140 ℃ and the absolute pressure of 0.8MPa by using an acetic acid solution with the concentration of 85wt%, wherein the mass ratio of the plant fiber raw materials to the acetic acid solution is 1:8, and after the steaming is finished, carrying out solid-liquid separation to obtain steaming liquid and first-time steaming plant fiber raw materials;
(2) Using an acetic acid solution with the concentration of 85wt% to cook the plant fiber raw material for 3 hours under the conditions that the temperature is 130 ℃ and the absolute pressure is 0.4MPa, wherein the mass ratio of the plant fiber raw material for the first time to the acetic acid solution is 1:8, and performing solid-liquid separation after the cooking is finished to obtain cooking liquid and the plant fiber raw material for the second time;
(3) Alternately washing the plant fiber raw material obtained in the step (2) for 6 times by using an acetic acid solution with the concentration of 85wt% and water to obtain a treated plant fiber raw material and an acetic acid washing solution;
(4) Recovering the cooking liquid obtained in the step (1), the cooking liquid obtained in the step (2) and the acetic acid washing liquid obtained in the step (3) respectively and independently, wherein the recovery treatment temperature of the cooking liquid obtained in the step (1) and the cooking liquid obtained in the step (2) is 100 ℃, the vacuum degree is-0.05 MPa, and the concentration multiple is 6 times to obtain acetic acid and a concentrated solution; when the acetic acid washing liquid obtained in the step (3) is recovered, the temperature for concentrating and recovering the acetic acid is 100 ℃, the vacuum degree is-0.05 MPa, and the concentration multiple is 15 times, so that the acetic acid is obtained; the obtained acetic acid is reused in the step (1), the step (2) and the step (3);
(5) Diluting the concentrated solution obtained in the step (4) with water at 70 ℃ with a dilution factor of 12 times, and carrying out solid-liquid separation to obtain sugar solution and lignin.
In the embodiment, the cooking liquid and the washing liquid are concentrated, and the treatment cost and the environmental pressure are reduced by recycling the acetic acid; and the concentrated solution can be used for extracting sugar and/or lignin, so that the economic benefit of enterprises is improved.
Example 2
The embodiment provides a method for treating plant fiber raw materials by acetic acid solution, wherein the plant fiber raw materials are hardwoods, and the method comprises the following steps:
(1) Steaming plant fiber raw materials for 6 hours at 130 ℃ and absolute pressure of 0.4MPa by using acetic acid solution with concentration of 75wt%, wherein the mass ratio of the plant fiber raw materials to the acetic acid solution is 1:12, and after the steaming is finished, carrying out solid-liquid separation to obtain steaming liquid and first-time steaming plant fiber raw materials;
(2) Using 75wt% acetic acid solution to cook the first-time cooked plant fiber raw material for 2 hours at the temperature of 140 ℃ and the absolute pressure of 0.3MPa, wherein the mass ratio of the first-time cooked plant fiber raw material to the acetic acid solution is 1:12, and performing solid-liquid separation after the cooking is finished to obtain cooking liquid and second-time cooked plant fiber raw material;
(3) Alternately washing the plant fiber raw material obtained in the step (2) for 4 times by using an acetic acid solution with the concentration of 90 weight percent and water to obtain a treated plant fiber raw material and an acetic acid washing solution;
(4) Recovering the cooking liquid obtained in the step (1), the cooking liquid obtained in the step (2) and the acetic acid washing liquid obtained in the step (3) respectively and independently; concentrating the cooking liquor obtained in the step (1) to recover acetic acid at 80 ℃, wherein the vacuum degree is-0.08 MPa, and the concentration multiple is 8 times to obtain acetic acid and concentrated liquor; concentrating the cooking liquor obtained in the step (2) to recover acetic acid at 80 ℃, wherein the vacuum degree is-0.08 MPa, and the concentration multiple is 8 times to obtain acetic acid and concentrated liquor; recovering the washing liquid obtained in the step (3) at 80 ℃, wherein the vacuum degree is-0.08 MPa, and the concentration multiple is 10 times to obtain acetic acid; the obtained acetic acid is reused in the step (1), the step (2) and the step (3);
(5) Diluting the concentrated solution obtained in the step (4) with water at 50 ℃ with the dilution multiple of 8 times, and carrying out solid-liquid separation to obtain sugar solution and lignin.
In the embodiment, the cooking liquid and the washing liquid are concentrated, and the treatment cost and the environmental pressure are reduced by recycling the acetic acid; and the concentrated solution can be used for extracting sugar and/or lignin, so that the economic benefit of enterprises is improved.
Example 3
The embodiment provides a method for treating plant fiber raw materials by acetic acid solution, wherein the plant fiber raw materials are corn stalks, and the method comprises the following steps:
(1) Using acetic acid solution with the concentration of 100wt% to steam plant fiber raw materials for 2 hours under the conditions that the temperature is 160 ℃ and the absolute pressure is 0.3MPa, wherein the mass ratio of the plant fiber raw materials to the acetic acid solution is 1:4, and performing solid-liquid separation after finishing the steam, so as to obtain steam liquor and first steam plant fiber raw materials;
(2) Using acetic acid solution with the concentration of 100wt% to cook the plant fiber raw material for 4 hours under the conditions that the temperature is 120 ℃ and the absolute pressure is 0.2MPa, wherein the mass ratio of the plant fiber raw material to the acetic acid solution for the first time is 1:4, and after the cooking is finished, carrying out solid-liquid separation to obtain cooking liquid and the plant fiber raw material for the second time;
(3) Alternately washing the plant fiber raw material obtained in the step (2) for 8 times by using an acetic acid solution with the concentration of 80 weight percent and water to obtain a treated plant fiber raw material and an acetic acid washing solution;
(4) Recovering the cooking liquid obtained in the step (1), the cooking liquid obtained in the step (2) and the acetic acid washing liquid obtained in the step (3) respectively and independently; concentrating the cooking liquor obtained in the step (1) to recover acetic acid at 120 ℃, wherein the vacuum degree is-0.03 MPa, and the concentration multiple is 4 times to obtain acetic acid and concentrated liquor; concentrating the cooking liquor obtained in the step (2) to recover acetic acid at 120 ℃, wherein the vacuum degree is-0.03 MPa, and the concentration multiple is 4 times to obtain acetic acid and concentrated liquor; concentrating the washing liquid obtained in the step (3) to recover acetic acid at 110 ℃, wherein the vacuum degree is-0.03 MPa, and the concentration multiple is 20 times to obtain acetic acid; the obtained acetic acid is reused in the step (1), the step (2) and the step (3);
(5) Diluting the concentrated solution obtained in the step (4) with water at 80 ℃ to obtain a dilution factor of 16 times, and carrying out solid-liquid separation to obtain sugar solution and lignin.
In the embodiment, the cooking liquid and the washing liquid are concentrated, and the treatment cost and the environmental pressure are reduced by recycling the acetic acid; and the concentrated solution can be used for extracting sugar and/or lignin, so that the economic benefit of enterprises is improved.
Example 4
The embodiment provides a method for treating plant fiber raw materials by acetic acid solution, wherein the plant fiber raw materials are shrubs, and the method comprises the following steps:
(1) Steaming plant fiber raw materials for 8 hours at the temperature of 115 ℃ and the absolute pressure of 0.2MPa by using acetic acid solution with the concentration of 60wt percent, wherein the mass ratio of the plant fiber raw materials to the acetic acid solution is 1:3, and replacing the steaming liquid by using the acetic acid solution with the concentration of 60wt percent after the steaming is finished, wherein the mass ratio of the acetic acid solution to the plant fiber raw materials is 3:1;
(2) Directly cooking the mixed liquor obtained after the replacement for 0.5h at the temperature of 150 ℃ and the absolute pressure of 0.6MPa, and carrying out solid-liquid separation after the cooking is finished to obtain cooking liquor and a second-time cooking plant fiber raw material;
(3) Alternately washing the plant fiber raw material obtained in the step (2) for 2 times by using an acetic acid solution with the concentration of 100 weight percent and water to obtain a treated plant fiber raw material and an acetic acid washing solution;
(4) The cooking liquid obtained in the step (1), the cooking liquid obtained in the step (2) and the washing liquid obtained in the step (3) are respectively and independently recycled; concentrating the cooking liquid obtained in the step (1) to recover acetic acid at 130 ℃, wherein the vacuum degree is 0MPa, and the concentration multiple is 3 times to obtain acetic acid and concentrated liquid; concentrating the cooking liquid obtained in the step (2) to recover acetic acid at 130 ℃, wherein the vacuum degree is 0MPa, and the concentration multiple is 3 times to obtain acetic acid and concentrated liquid; recovering the washing liquid obtained in the step (3) at 130 ℃, wherein the vacuum degree is 0MPa, and the concentration multiple is 5 times to obtain acetic acid; the obtained acetic acid is reused in the step (1), the step (2) and the step (3);
(5) Diluting the concentrated solution obtained in the step (4) with water at 40 ℃ to obtain a dilution factor of 4 times, and carrying out solid-liquid separation to obtain sugar solution and lignin.
In the embodiment, the cooking liquid and the washing liquid are concentrated, and the treatment cost and the environmental pressure are reduced by recycling the acetic acid; and the concentrated solution can be used for extracting sugar and/or lignin, so that the economic benefit of enterprises is improved.
Example 5
The embodiment provides a method for treating plant fiber raw materials by acetic acid solution, wherein the plant fiber raw materials are bagasse, and the method comprises the following steps:
(1) Steaming plant fiber raw materials for 1h at 180 ℃ under the absolute pressure of 1MPa by using acetic acid solution with the concentration of 70wt%, wherein the mass ratio of the plant fiber raw materials to the acetic acid solution is 1:15, and replacing the steaming liquid by using the acetic acid solution with the concentration of 70wt% after the steaming is finished, wherein the mass ratio of the acetic acid solution to the plant fiber raw materials is 15:1;
(2) Directly cooking the mixed solution obtained after the replacement for 5 hours at the temperature of 100 ℃ and the absolute pressure of 0.1MPa, and performing solid-liquid separation after the cooking is finished to obtain cooking solution and second-time cooking plant fiber raw materials;
(3) Alternately washing the plant fiber raw material obtained in the step (2) for 10 times by using an acetic acid solution with the concentration of 70 weight percent and water to obtain a treated plant fiber raw material and an acetic acid washing solution;
(4) The cooking liquid obtained in the step (1), the cooking liquid obtained in the step (2) and the washing liquid obtained in the step (3) are respectively and independently recycled; concentrating the cooking liquor obtained in the step (1) to recover acetic acid at 50 ℃, wherein the vacuum degree is-0.1 MPa, and the concentration multiple is 10 times to obtain acetic acid and concentrated liquor; concentrating the cooking liquor obtained in the step (2) to recover acetic acid at 50 ℃, wherein the vacuum degree is-0.01 MPa, and the concentration multiple is 10 times to obtain acetic acid and concentrated liquor; recovering the washing liquid obtained in the step (3) at 50 ℃, wherein the vacuum degree is-0.1 MPa, and the concentration multiple is 30 times to obtain acetic acid; the obtained acetic acid is reused in the step (1), the step (2) and the step (3);
(5) Diluting the concentrated solution obtained in the step (4) with water at 100 ℃ to obtain a dilution factor of 20 times, and carrying out solid-liquid separation to obtain sugar solution and lignin.
In the embodiment, the cooking liquid and the washing liquid are concentrated, and the treatment cost and the environmental pressure are reduced by recycling the acetic acid; and the concentrated solution can be used for extracting sugar and/or lignin, so that the economic benefit of enterprises is improved.
Example 6
The embodiment provides a method for treating plant fiber raw materials by acetic acid solution, wherein the plant fiber raw materials are bamboo, and the method comprises the following steps:
(1) Steaming plant fiber raw materials for 4 hours at the temperature of 140 ℃ and the absolute pressure of 0.8MPa by using an acetic acid solution with the concentration of 85wt%, wherein the mass ratio of the plant fiber raw materials to the acetic acid solution is 1:8, and after the steaming is finished, carrying out solid-liquid separation to obtain steaming liquid and first-time steaming plant fiber raw materials;
(2) Using an acetic acid solution with the concentration of 85wt% to cook the plant fiber raw material for 3 hours under the conditions that the temperature is 130 ℃ and the absolute pressure is 0.4MPa, wherein the mass ratio of the plant fiber raw material for the first time to the acetic acid solution is 1:8, and performing solid-liquid separation after the cooking is finished to obtain cooking liquid and the plant fiber raw material for the second time;
(3) Alternately washing the plant fiber raw material obtained in the step (2) for 6 times by using an acetic acid solution with the concentration of 85wt% and ethyl acetate, and desolventizing the washed plant fiber raw material at 100 ℃ to obtain a treated plant fiber raw material and a mixed washing solution;
(4) Recovering the cooking liquid obtained in the step (1) and the cooking liquid obtained in the step (2) respectively and independently to obtain acetic acid and concentrated solution, wherein the obtained acetic acid is reused in the step (1), the step (2) and the step (3); concentrating the cooking liquor obtained in the step (1) to recover acetic acid at a temperature of 100 ℃, wherein the vacuum degree is-0.05 MPa, and the concentration multiple is 6 times; concentrating the cooking liquor obtained in the step (2) to recover acetic acid at a temperature of 100 ℃, wherein the vacuum degree is-0.05 MPa, and the concentration multiple is 6 times; rectifying the mixed washing liquid obtained in the step (3), and separating to obtain acetic acid and acetic acid extractant ethyl acetate, wherein the acetic acid is recycled in the step (1), the step (2) and the step (3), and the acetic acid extractant ethyl acetate is recycled in the step (3);
(5) Diluting the concentrated solution obtained in the step (4) with water at 70 ℃ with a dilution factor of 12 times, and carrying out solid-liquid separation to obtain sugar solution and lignin.
In the embodiment, the cooking liquid and the washing liquid are concentrated, and the treatment cost and the environmental pressure are reduced by recycling the acetic acid; and the concentrated solution can be used for extracting sugar and/or lignin, so that the economic benefit of enterprises is improved.
Example 7
This example provides a method for treating a plant fiber raw material with an acetic acid solution, which is the same as example 6, except that ethyl acetate is replaced with n-propyl acetate, and the desolventizing temperature in step (3) is 150 ℃.
In the embodiment, the cooking liquid and the washing liquid are concentrated, and the treatment cost and the environmental pressure are reduced by recycling the acetic acid; and the concentrated solution can be used for extracting sugar and/or lignin, so that the economic benefit of enterprises is improved.
Example 8
This example provides a method for treating a plant fiber raw material with an acetic acid solution, which is the same as example 6, except that ethyl acetate is replaced with isobutyl acetate, and the desolventizing temperature in step (3) is 60 ℃.
In the embodiment, the cooking liquid and the washing liquid are concentrated, and the treatment cost and the environmental pressure are reduced by recycling the acetic acid; and the concentrated solution can be used for extracting sugar and/or lignin, so that the economic benefit of enterprises is improved.
Example 9
This example provides a method for treating a plant fiber raw material with an acetic acid solution, which is the same as example 6, except that ethyl acetate is replaced with ethyl n-valerate.
In the embodiment, the cooking liquid and the washing liquid are concentrated, and the treatment cost and the environmental pressure are reduced by recycling the acetic acid; and the concentrated solution can be used for extracting sugar and/or lignin, so that the economic benefit of enterprises is improved.
Example 10
This example provides a method for treating a plant fiber raw material with an acetic acid solution, which is the same as example 6, except that ethyl acetate is replaced with glyceryl acetate.
In the embodiment, the cooking liquid and the washing liquid are concentrated, and the treatment cost and the environmental pressure are reduced by recycling the acetic acid; and the concentrated solution can be used for extracting sugar and/or lignin, so that the economic benefit of enterprises is improved.
Example 11
This example provides a method for treating a lignocellulosic feedstock with an acetic acid solution, the method being the same as in example 1 except that the cooking temperature in step (1) is 100 ℃.
Example 12
The present example provides a method for treating a lignocellulosic feedstock with an acetic acid solution, the method being the same as in example 1 except that the mass ratio of the plant fiber feedstock to the acetic acid solution in step (1) is 1:2.
Example 13
This example provides a process for treating a lignocellulosic feedstock with an acetic acid solution, the process being the same as in example 1 except that the absolute pressure of the digestion in step (1) is 1.2 MPa.
Example 14
This example provides a process for treating a lignocellulosic feedstock with an acetic acid solution, the process being the same as in example 1 except that the cooking temperature in step (2) is 90 ℃.
Example 15
This example provides a process for treating a lignocellulosic feedstock with an acetic acid solution, the process being the same as in example 1 except that the cooking temperature in step (2) is 170 ℃.
Example 16
This example provides a process for treating a lignocellulosic feedstock with an acetic acid solution, the process being the same as in example 1 except that the absolute pressure of the digestion in step (2) is 0.7 MPa.
Example 17
The present example provides a method for treating a lignocellulosic feedstock with an acetic acid solution, the method being the same as in example 1 except that the mass ratio of the first cooked plant fiber feedstock to the acetic acid solution in step (2) is 1:2.
Comparative example 1
The comparative example provides a method for treating plant fiber raw material by acetic acid solution, wherein the plant fiber raw material is bagasse, and the method comprises the following steps:
(1) Steaming plant fiber raw materials for 4 hours at the temperature of 140 ℃ and the absolute pressure of 0.8MPa by using an acetic acid solution with the concentration of 85wt%, wherein the mass ratio of the plant fiber raw materials to the acetic acid solution is 1:8, and after the steaming is finished, carrying out solid-liquid separation to obtain steaming liquid and the steamed plant fiber raw materials;
(2) Alternately washing the steamed plant fiber raw material obtained in the step (1) with 85wt% acetic acid solution and water for 6 times to obtain a treated plant fiber raw material; collecting an acetic acid washing solution after washing with an acetic acid solution;
(3) Concentrating the cooking liquid obtained in the step (1) and the acetic acid washing liquid obtained in the step (2) to recover acetic acid to obtain acetic acid and a concentrated solution, wherein the obtained acetic acid is reused in the step (1) and the step (2), and the obtained concentrated solution is used for extracting sugar and/or lignin; concentrating the cooking liquor obtained in the step (1) to recover acetic acid at a temperature of 100 ℃, wherein the vacuum degree is-0.05 MPa, and the concentration multiple is 6 times; concentrating the washing liquid obtained in the step (2) to recover acetic acid at 100 ℃, wherein the vacuum degree is-0.05 MPa, and the concentration multiple is 6 times;
(4) Diluting the concentrated solution obtained in the step (4) with water at 70 ℃ with a dilution factor of 12 times, and carrying out solid-liquid separation to obtain sugar solution and lignin.
Comparative example 2
This comparative example provides a method of treating a plant fiber raw material, which is the same as example 1, except that the acetic acid solution is replaced with a formic acid solution of equal mass fraction.
Comparative example 3
This comparative example provides a method of treating a plant fiber raw material, which is the same as example 1, except that the acetic acid solution is replaced with an equal mass fraction of propionic acid solution.
The cellulose extraction rate, lignin extraction rate and sugar extraction rate of the treated plant fiber raw materials obtained in examples 1 to 17 and comparative examples 1 to 3 were measured (the ratio of the weights of the extracted cellulose, lignin and sugar to the weights of the three components in the raw materials, respectively, are the extraction rates), and the obtained results are shown in table 1.
The lignin, sugar and cellulose component contents in the raw materials are measured according to the methods of GB/T10337-2008 determination of acid-soluble lignin in paper making raw materials and paper pulp, GB/T2677.8-1994 determination of acid-insoluble lignin content in paper making raw materials, GB/T2677.9-1994 determination of pentose content in paper making raw materials, GB/T12033-2008 determination of gas chromatography of sugar components in paper making raw materials and paper pulp and the like, so that the theoretical weights of cellulose, lignin and sugar in the raw materials are obtained.
The weights of the extracted cellulose, lignin and sugar are calculated from the weights of the products obtained after treatment, wherein the lignin products can be directly weighed, the sugar content in sugar liquid obtained by analysis is calculated, and the cellulose products are measured and calculated on the treated fiber raw materials according to a raw material measuring method.
TABLE 1
Figure BDA0002471835020000201
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Figure BDA0002471835020000211
As can be seen from examples 1 to 10, the method for treating plant fiber raw materials with acetic acid solution provided by the invention can enable the cellulose extraction rate to reach 87.65-93.56%; the lignin extraction rate reaches 86.04-93.51%; the sugar extraction rate reaches 88.06-93.89%.
As can be seen from example 11, when the temperature of the first cook was lower, the lignin extraction was reduced from 93.44% to 83.43% and the sugar extraction was reduced from 92.36% to 86.52% although the cellulose extraction was increased from 87.65% to 91.01%.
As is clear from example 12, when the amount of acetic acid used for the first cooking was small, the extraction rate of cellulose was increased from 87.65% to 93.33%, but the extraction rate of lignin was decreased from 93.44% to 81.61%, and the extraction rate of sugar was decreased from 92.36% to 87.49%. And when more acetic acid is used for cooking, the waste of the acetic acid can be caused, and the cooking cost is increased.
From example 13, it is seen that when the pressure of the first cooking is too high, the extraction rate of sugar is increased from 92.36% to 93.57%, but the extraction rate of cellulose is decreased from 87.65% to 82.18%, and the extraction rate of lignin is decreased from 93.44% to 92.87%; further, the increase in pressure causes an increase in cost, and it is found that when the pressure of the first steam boiling is too high, it is impossible to maintain a high extraction rate of cellulose, lignin and sugar at low cost.
As is clear from example 14, when the temperature of the second cooking was low, the cooking cost was reduced and the cellulose extraction rate was increased from 87.65% to 93.64%, but the lignin extraction rate was decreased from 93.44% to 80.04%, the sugar extraction rate was decreased from 92.36% to 86.12%, and the lignin and sugar extraction rates were decreased more.
As is clear from example 15, when the temperature of the second cooking was higher, although lignin extraction rate and sugar extraction rate were not changed much, the cooking problem was increased to increase the cooking cost, and the cellulose extraction rate was reduced from 87.65% to 79.97%.
It is clear from examples 14 and 15 that when the temperature of the second cooking is too low or too high, it is not advantageous to maintain high extraction rates of cellulose, lignin and sugar at low cost.
As is clear from example 16, when the pressure of the second cooking was higher, the cost of the second cooking was increased, but the cellulose extraction was reduced from 87.65% to 83.58%, the lignin extraction was reduced from 93.44% to 90.89%, and the sugar extraction was reduced from 92.36% to 91.62%.
As is clear from example 17, when the amount of acetic acid used for the second cooking was small, the cellulose extraction rate was increased from 87.65% to 90.72%, but the lignin extraction rate was decreased from 93.44% to 86.45% and the sugar extraction rate was decreased from 92.36% to 87.1%.
As is clear from comparative example 1, when the cooking was performed only once, the cellulose extraction rate was reduced from 87.65% to 81.62%, the lignin extraction rate was reduced from 93.44% to 86.33%, and the sugar extraction rate was reduced from 92.36% to 91.82%.
As is clear from comparative examples 2 to 3, the three components could not be extracted well by using formic acid or propionic acid solutions.
In summary, the high-concentration acetic acid solution is used for treating the plant fiber raw material, so that no additional catalyst is needed, the types and the use amount of solvents are reduced, and the treatment cost and the risk of environmental pollution are reduced; the acetic acid solution is used for treating the plant fiber raw material, and the acetic acid solution is concentrated, recycled and used, so that the production water is reduced, the production cost is reduced, the pollution to the environment is reduced, and the energy is saved and the environment is protected; in addition, the invention only uses acetic acid solution to treat the plant fiber raw material, and can classify lignin, cellulose and sugar in the plant fiber raw material without adding other auxiliary agents, thereby realizing the efficient extraction of the plant fiber raw material.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.

Claims (1)

1. A method for treating plant fiber raw materials with an acetic acid solution, comprising the steps of:
(1) Using 75-95wt% acetic acid solution to cook plant fiber raw material for 2-6h at 130-160 deg.c and absolute pressure of 0.3-0.8MPa, wherein the mass ratio of plant fiber raw material to acetic acid solution is 1 (4-12), and solid-liquid separation is carried out after the cooking is completed to obtain cooking liquid and first-time cooking plant fiber raw material; or, after the cooking is finished, replacing the cooking liquid by using acetic acid solution with the concentration of 75-95wt%, wherein the mass ratio of the replaced acetic acid solution to the plant fiber raw material is (4-12): 1; the plant fiber raw material comprises woody biomass and/or graminaceous biomass; the woody biomass comprises any one or a combination of at least two of hardwood, softwood or shrubs; the graminaceous biomass comprises any one or a combination of at least two of bagasse, bamboo, straw, wheat straw, corn straw or reed;
(2) Using acetic acid solution with the concentration of 75-95wt% to cook the plant fiber raw material for 2-4 hours under the conditions that the temperature is 120-150 ℃ and the absolute pressure is 0.2-0.6MPa, wherein the mass ratio of the plant fiber raw material to the acetic acid solution for the first time is 1 (4-12); or directly steaming the mixed solution obtained after the replacement for 2-4 hours under the conditions that the temperature is 120-150 ℃ and the absolute pressure is 0.2-0.6 MPa; after the cooking is finished, carrying out solid-liquid separation to obtain cooking liquid and a second-time cooking plant fiber raw material;
(3) Alternately washing the second steamed plant fiber raw material obtained in the step (2) for 2-10 times by using an acetic acid solution with the concentration of 80-100wt% and an acetic acid extractant, and desolventizing the washed plant fiber raw material at 60-150 ℃ to obtain a treated plant fiber raw material and a mixed washing liquid;
(4) Recovering the cooking liquid obtained in the step (1), the cooking liquid obtained in the step (2) and the mixed washing liquid obtained in the step (3) respectively and independently, wherein the temperature for recovering the cooking liquid obtained in the step (1) and the cooking liquid obtained in the step (2) is 50-130 ℃, the vacuum degree is-0.1-0 MPa, and the multiple of concentration is 3-10 times, so as to obtain acetic acid and concentrated solution; recycling the mixed washing liquid obtained in the step (3);
The recovery treatment comprises rectifying and separating the mixed washing liquid obtained in the step (3) to obtain acetic acid and an acetic acid extractant; the acetic acid extractant is an ester acetic acid extractant; the ester acetic acid extractant comprises any one or a combination of at least two of ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, n-ethyl valerate and glyceryl acetate;
(5) Separating lignin from sugar solution from the concentrated solution obtained in the step (4) at 40-100 ℃;
no additional catalyst is needed in the process.
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