CN113416565A - Method for promoting pyrolysis saccharification by pretreating biomass raw material with simulated low cosolvent and application - Google Patents
Method for promoting pyrolysis saccharification by pretreating biomass raw material with simulated low cosolvent and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/08—Non-mechanical pretreatment of the charge, e.g. desulfurization
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/08—Non-mechanical pretreatment of the charge, e.g. desulfurization
- C10B57/10—Drying
-
- 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
-
- 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
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Abstract
The invention discloses a method for promoting pyrolysis saccharification by pretreating a biomass raw material by using an imitation low cosolvent and application. The method comprises the following steps: (1) after mixing the biomass light oil and choline chloride, heating, stirring and dissolving to form a uniform solution, thereby obtaining an imitation eutectic solvent system; (2) adding a biomass raw material into an imitation eutectic solvent system, stirring and reacting at 80-120 ℃, after the reaction is finished, carrying out solid-liquid separation, taking a solid, washing and drying to obtain a pretreated solid product; (3) and (3) pyrolyzing the pretreated solid product in a protective gas atmosphere at 450-600 ℃, condensing and collecting the pyrolyzed volatile components, and thus obtaining the pyrolyzed bio-oil. According to the invention, the biomass light oil derived from biomass is used for replacing a hydrogen bond donor in the eutectic solvent, so that the cost of the eutectic solvent system is reduced, the biomass can be promoted to be pyrolyzed and saccharified when the biomass light oil is used for pretreating the biomass, and the enrichment of the levoglucosan in the pyrolysis oil is facilitated.
Description
Technical Field
The invention belongs to the field of biomass recycling, and particularly relates to a method for promoting pyrolysis saccharification by pretreating a biomass raw material by using an imitation low cosolvent and application.
Background
With the consumption of fossil fuels, environmental problems and non-renewable energy problems are increasingly prominent. Lignocellulose is considered an ideal alternative energy source and is receiving increasing attention. In addition, millions of tons of corn stover are produced annually in the world, creating serious environmental problems. From the viewpoint of environment and economy, realizing the recycling of agricultural and forestry wastes is a necessary means for realizing sustainable development. At present, the lignocellulose resources can be converted into bio-oil and other fine chemical products by thermo-chemical methods such as pyrolysis, gasification, combustion and the like.
Generally, lignocellulose is rapidly pyrolyzed at a medium temperature (450-600 ℃), under an inert atmosphere and under a normal pressure working condition, so that the cellulose can be promoted to generate levoglucosan (levoglucosan) through homolytic cracking, heterolytic cracking, synergistic fracture and the like, and the levoglucosan is a main product of rapid pyrolysis of the lignocellulose. The levoglucosan can be directly metabolized by microorganisms, and the fermentation effect can be comparable with that of glucose, so that the levoglucosan is a new sugar source with great development potential. The fast pyrolysis process is expected to make up the deficiency of enzyme or acid hydrolysis technology, and has the advantages of low cost, fast reaction, high sugar concentration and the like. In addition, the levoglucosan is an important monomer for synthesizing a stereo compound, and can be used as a chiral synthon to synthesize resin, medicaments, high polymers and related products. The fast pyrolysis oil prepared by biomass pyrolysis has good commercial application potential. However, during fast pyrolysis of lignocellulose, the presence of ash and lignin in lignocellulose promotes the formation of small molecule compounds at the expense of levoglucosan. The low content of levoglucosan increases the cost of subsequent product separation and purification, thereby impairing its economic feasibility. Therefore, improving the selectivity of extracting levoglucosan from lignocellulose is the most important problem for promoting the development of pyrolytic saccharification.
Conventional pretreatments such as acid washing, alkali washing, ionic liquids, etc., while effective in overcoming these problems to improve the quality of pyrolysis oils, have their own drawbacks that limit widespread use. The Deep Eutectic Solvent (DES) is used as a substitute of ILS, and has the unique advantages of simple preparation, low cost, no toxicity, biodegradability and the like. Since the DESs can effectively destroy the cross-linked structure of lignocellulose, the effect of separating carbohydrate (i.e., cellulose and hemicellulose) and lignin is achieved, which is considered as an environmentally friendly solvent for pretreating lignocellulose. Typically, DESs are formed by complexing a Hydrogen Bond Acceptor (HBA) with a Hydrogen Bond Donor (HBD), such as acetic acid + choline chloride, phenol + choline chloride, and the like. The production of these hydrogen donors often requires the consumption of fossil fuels and complex reaction pathways.
Biomass-derived biomass light oil (BL oil) is a mixture composed of oxygenates and aromatics, and acetic acid and phenol are the main components of BL oil. However, to date, there has been no report on the replacement of hydrogen bond donors in low eutectic solvents with biomass-derived light biomass oils to reduce the cost of eutectic solvent systems and for pretreating biomass to facilitate its pyrolytic saccharification.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method for promoting pyrolysis saccharification by pretreating a biomass raw material by using an imitation low cosolvent.
Another object of the present invention is to provide an application of the method for promoting pyrolysis saccharification by utilizing simulated low cosolvent pretreatment of biomass raw material.
The purpose of the invention is realized by the following technical scheme:
a method for promoting pyrolysis saccharification by utilizing simulated low cosolvent pretreatment biomass raw materials comprises the following steps:
(1) after mixing the biomass light oil and choline chloride, heating, stirring and dissolving to form a uniform solution, thereby obtaining an imitation eutectic solvent system;
(2) adding a biomass raw material into the simulated eutectic solvent system obtained in the step (1), stirring and reacting at 80-120 ℃, after the reaction is finished, carrying out solid-liquid separation, taking a solid, washing and drying to obtain a pretreated solid product;
(3) and (3) pyrolyzing the pretreated solid product obtained in the step (2) in a protective gas atmosphere at 450-600 ℃, condensing and collecting the pyrolyzed volatile components to obtain the (levoglucosan-rich) pyrolyzed bio-oil.
The mass ratio of the biomass light oil to the choline chloride in the step (1) is (0.8:1) - (4: 1); preferably (2:1) to (3: 1); more preferably 2: 1.
The heating temperature in the step (1) is 60 +/-5 ℃.
The stirring conditions in the step (1) are as follows: stirring at 200-400 r/min for 10-60 min; preferably: stirring at 300r/min for 30 min.
The biomass raw material in the step (2) comprises lignocellulose and/or agricultural and forestry waste containing lignocellulose; preferably corn stover.
The particle size of the corn straw is more than 100 meshes.
The mass ratio of the biomass raw material to the simulated eutectic solvent system in the step (2) is 1: 10-20; preferably 1: 20.
the reaction temperature in the step (2) is preferably 100-120 ℃; more preferably 120 deg.c.
The stirring conditions in the step (2) are as follows: stirring for 5-10 h at 200-400 r/min; preferably: stirring at 300r/min for 5 h.
The solid-liquid separation in the step (2) is preferably realized by vacuum filtration.
And (3) washing in the step (2) is to sequentially use ethanol, acetone solution and distilled water for washing.
The acetone solution is 40% by volume.
The drying conditions in the step (2) are as follows: drying in an oven at 80-110 ℃ for 12-24 h; preferably: drying at 105 ℃ for 24 h.
The temperature of the pyrolysis described in step (3) is preferably 500 ℃.
The pyrolysis time in the step (3) is 30-60 min; preferably 30 min.
The protective gas in the step (3) is preferably nitrogen; preferably, the flow rate of the nitrogen is 100-600 ml/min; more preferably, nitrogen gas at a gas flow rate of 550 ml/min.
The method for pretreating the biomass raw material by using the simulated low cosolvent to promote pyrolysis saccharification is applied to agricultural and forestry waste resource recovery or preparation of pyrolysis bio-oil.
The pyrolytic bio-oil is pyrolytic bio-oil rich in levoglucosan; preferably pyrolytic bio-oil containing greater than 30mg/g L-glucan; more preferably a pyrolyzed bio-oil containing greater than 40mg/g levoglucosan; more preferably, the pyrolysis bio-oil contains 50-60 mg/g.
Compared with the prior art, the invention has the following advantages and effects:
1. the invention adopts a new organic solvent-simulated eutectic solvent system, wherein the biomass light oil is a direct pyrolysis product of natural lignocellulose, and because the biomass-derived pyrolysis oil has the defects of high oxygen content, acid corrosion, low calorific value, complex components and the like, the biomass pyrolysis oil is abandoned in the form of waste, and the successful application of the biomass pyrolysis oil can not only avoid the pollution of the pyrolysis oil to the environment, but also realize the closed-loop concept of biorefinery (figure 1).
2. The method utilizes biomass-derived biomass light oil to replace a hydrogen bond donor in the low eutectic solvent, is favorable for reducing the cost of a eutectic solvent system, and can promote the pyrolysis saccharification of the biomass when used for pretreatment.
3. According to the method, the cornstalks are pretreated by using the biomass-derived eutectic solvent imitating system, so that lignin and hemicellulose can be decomposed at a low temperature, the recalcitrance of raw materials is reduced, alkali metals and alkaline earth metals (AAEMs) contained in lignocellulose can be effectively removed, the cellulose is prevented from undergoing a ring-opening reaction in the pyrolysis process, and the enrichment of levoglucosan in pyrolysis oil is realized.
Drawings
FIG. 1 is a technical scheme of the process of the present invention.
FIG. 2 is a statistical chart of the proportion of each component in the biomass light oil.
Fig. 3 is a graph of the main chemical product content of biomass light oil.
FIG. 4 is a product distribution diagram of different simulated low co-solvent pretreatment conditions on cornstalk pyrolysis oil.
FIG. 5 is a product profile of three different pretreatments on cornstalk pyrolysis oil.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated. The test methods in the following examples, in which specific experimental conditions are not specified, are generally performed according to conventional experimental conditions or according to the experimental conditions recommended by the manufacturer. Unless otherwise specified, reagents and starting materials for use in the present invention may be obtained by conventional routes or commercially available.
The biomass light oil related in the embodiment of the invention is a pyrolysis oil prepared by fast pyrolysis of different sawdust mixtures, standing and filtering the pyrolysis oil, removing heavy oil and a water phase part to obtain an upper layer light oil part, wherein the water content is 39.80%, and the upper layer light oil part is purchased from Guangzhou Dison biomass energy company Limited. The component ratio of the biomass light oil is shown in figure 2, and the content of main chemical products is shown in figure 3.
The choline chloride involved in the examples of the present invention was purchased from Shanghai Michelin Biochemical technology Ltd.
The embodiment of the invention relates to cornstalks, namely cornstalks (which can be obtained by a conventional way), and before the cornstalks are pretreated, the cornstalks need to be crushed into 100 meshes of size, then the cornstalks are placed in an oven to be dried for 48 hours, and finally the cornstalks are collected for standby application.
Example 1
(1) Preparing an imitation eutectic solvent system: 66.67g of biomass light oil is put into a thick-wall pressure-resistant bottle, 53.33g of choline chloride is added, the mixture is placed in an oil bath kettle at 60 ℃, and the mixture is heated and reacts for 30min at the stirring speed of 300r/min until the choline chloride is dissolved to form a uniform solution.
(2) Pretreatment of corn stalk raw materials: according to the mass ratio of 1: 20, 6g of cornstalks are poured into 120g of the pseudo-eutectic solvent system prepared in the step (1) and reacted for 5 hours at the temperature of 120 ℃ at the stirring speed of 300 r/min. After the pretreatment is finished, the solid-liquid separation is realized by vacuum filtration, and the pretreated materials (solid residues) are washed by ethanol, 40% (v/v) acetone solution and distilled water in sequence until the filtrate is colorless and transparent. The solid residue was dried in an oven at 105 ℃ for 24 hours, and the obtained sample was named Bio-DES (0.8:1) (0.8:1 is the mass ratio of biomass light oil to choline chloride).
(3) And (3) pyrolysis saccharification: a0.5 g sample of the pretreated solid was placed in a quartz tube having a diameter of 35mm and a length of 500mm, and quartz wool was inserted into both ends of the tube so that the sample was located at the center of the tube. Then selecting high-purity nitrogen as a protector, wherein the flow rate of the nitrogen is 550mL/min, when the temperature of the tube furnace is heated to 500 ℃, quickly inserting the quartz tube into the furnace for keeping for 0.5h, then taking out the quartz tube, and cooling to the room temperature. The pyrolytic bio-oil is liquefied by a condensing device and collected in a serum bottle filled with acetone. The obtained pyrolysis bio-oil is named as cornstalk pyrolysis oil (0.8: 1).
Example 2
(1) Preparing an imitation eutectic solvent system: taking 60g of biomass light oil, putting the biomass light oil into a thick-wall pressure-resistant bottle, adding 60g of choline chloride, putting the bottle in an oil bath kettle at the temperature of 60 ℃, heating and reacting for 30min at the stirring speed of 300r/min until the choline chloride is dissolved to form a uniform solution.
(2) Pretreatment of corn stalk raw materials: according to the mass ratio of 1: 20, 6g of cornstalks are poured into 120g of the pseudo-eutectic solvent system prepared in the step (1) and reacted for 5 hours at the temperature of 120 ℃ at the stirring speed of 300 r/min. After the pretreatment is finished, the solid-liquid separation is realized through vacuum filtration, and the pretreated materials are washed by ethanol, 40% (v/v) acetone solution and distilled water in sequence until the filtrate is colorless and transparent. The solid residue was dried in an oven at 105 ℃ for 24 hours, and the obtained sample was named Bio-DES (1: 1).
(3) And (3) pyrolysis saccharification: a0.5 g sample of the pretreated solid was placed in a quartz tube having a diameter of 35mm and a length of 500mm, and quartz wool was inserted into both ends of the tube so that the sample was located at the center of the tube. Then selecting high-purity nitrogen as a protector, wherein the flow rate of the nitrogen is 550mL/min, when the temperature of the tube furnace is heated to 500 ℃, quickly inserting the quartz tube into the furnace for keeping for 0.5h, then taking out the quartz tube, and cooling to the room temperature. The pyrolytic bio-oil is liquefied by a condensing device and collected in a serum bottle filled with acetone. The obtained pyrolysis bio-oil is named as cornstalk pyrolysis oil (1: 1).
Example 3
(1) Preparing an imitation eutectic solvent system: 80g of biomass light oil is put into a thick-wall pressure-resistant bottle, 40g of choline chloride is added, the mixture is placed in an oil bath kettle at the temperature of 60 ℃, and the mixture is heated and reacts for 30min at the stirring speed of 300r/min until the choline chloride is dissolved to form a uniform solution.
(2) Pretreatment of corn stalk raw materials: according to the mass ratio of 1: 20, 6g of cornstalks are poured into 120g of the pseudo-eutectic solvent system prepared in the step (1) and reacted for 5 hours at the temperature of 120 ℃ at the stirring speed of 300 r/min. After the pretreatment is finished, the solid-liquid separation is realized through vacuum filtration, and the pretreated materials are washed by ethanol, 40% (v/v) acetone solution and distilled water in sequence until the filtrate is colorless and transparent. The solid residue was dried in an oven at 105 ℃ for 24 hours, and the obtained sample was named Bio-DES (2: 1).
(3) And (3) pyrolysis saccharification: a0.5 g sample of the pretreated solid was placed in a quartz tube having a diameter of 35mm and a length of 500mm, and quartz wool was inserted into both ends of the tube so that the sample was located at the center of the tube. Then selecting high-purity nitrogen as a protector, wherein the flow rate of the nitrogen is 550mL/min, when the temperature of the tube furnace is heated to 500 ℃, quickly inserting the quartz tube into the furnace for keeping for 0.5h, then taking out the quartz tube, and cooling to the room temperature. The pyrolytic bio-oil is liquefied by a condensing device and collected in a serum bottle filled with acetone. The obtained pyrolysis bio-oil is named as cornstalk pyrolysis oil (2: 1).
Example 4
(1) Preparing an imitation eutectic solvent system: taking 90g of biomass light oil, putting the biomass light oil into a thick-wall pressure-resistant bottle, adding 30g of choline chloride, putting the bottle in an oil bath kettle at the temperature of 60 ℃, heating and reacting for 30min at the stirring speed of 300r/min until the choline chloride is dissolved to form a uniform solution.
(2) Pretreatment of corn stalk raw materials: according to the mass ratio of 1: 20, 6g of cornstalks are poured into 120g of the pseudo-eutectic solvent system prepared in the step (1) and reacted for 5 hours at the temperature of 120 ℃ at the stirring speed of 300 r/min. After the pretreatment is finished, the solid-liquid separation is realized through vacuum filtration, and the pretreated materials are washed by ethanol, 40% (v/v) acetone solution and distilled water in sequence until the filtrate is colorless and transparent. The solid residue was dried in an oven at 105 ℃ for 24 hours, and the obtained sample was named Bio-DES (3: 1).
(3) And (3) pyrolysis saccharification: a0.5 g sample of the pretreated solid was placed in a quartz tube having a diameter of 35mm and a length of 500mm, and quartz wool was inserted into both ends of the tube so that the sample was located at the center of the tube. Then selecting high-purity nitrogen as a protector, wherein the flow rate of the nitrogen is 550mL/min, when the temperature of the tube furnace is heated to 500 ℃, quickly inserting the quartz tube into the furnace for keeping for 0.5h, then taking out the quartz tube, and cooling to the room temperature. The pyrolytic bio-oil is liquefied by a condensing device and collected in a serum bottle filled with acetone. The obtained pyrolysis bio-oil is named as cornstalk pyrolysis oil (3: 1).
Example 5
(1) Preparing an imitation eutectic solvent system: putting 96g of biomass light oil into a thick-wall pressure-resistant bottle, adding 24g of choline chloride, putting the bottle in an oil bath kettle at 60 ℃, heating and reacting for 30min at a stirring speed of 300r/min until the choline chloride is dissolved to form a uniform solution.
(2) Pretreatment of corn stalk raw materials: according to the mass ratio of 1: 20, 6g of cornstalks are poured into 120g of the pseudo-eutectic solvent system prepared in the step (1) and reacted for 5 hours at the temperature of 120 ℃ at the stirring speed of 300 r/min. After the pretreatment is finished, the solid-liquid separation is realized through vacuum filtration, and the pretreated materials are washed by ethanol, 40% (v/v) acetone solution and distilled water in sequence until the filtrate is colorless and transparent. The solid residue was dried in an oven at 105 ℃ for 24 hours, and the obtained sample was named Bio-DES (4: 1).
(3) And (3) pyrolysis saccharification: a0.5 g sample of the pretreated solid was placed in a quartz tube having a diameter of 35mm and a length of 500mm, and quartz wool was inserted into both ends of the tube so that the sample was located at the center of the tube. Then selecting high-purity nitrogen as a protector, wherein the flow rate of the nitrogen is 550mL/min, when the temperature of the tube furnace is heated to 500 ℃, quickly inserting the quartz tube into the furnace for keeping for 0.5h, then taking out the quartz tube, and cooling to the room temperature. The pyrolytic bio-oil is liquefied by a condensing device and collected in a serum bottle filled with acetone. The obtained pyrolysis bio-oil is named as cornstalk pyrolysis oil (4: 1).
Example 6
(1) Preparing an imitation eutectic solvent system: 80g of biomass light oil is put into a thick-wall pressure-resistant bottle, 40g of choline chloride is added, the mixture is placed in an oil bath kettle at the temperature of 60 ℃, and the mixture is heated and reacts for 30min at the stirring speed of 300r/min until the choline chloride is dissolved to form a uniform solution.
(2) Pretreatment of corn stalk raw materials: according to the mass ratio of 1: 20, 6g of cornstalks are poured into 120g of the pseudo-eutectic solvent system prepared in the step (1) and reacted for 5 hours at the temperature of 80 ℃ and the stirring speed of 300 r/min. After the pretreatment is finished, the solid-liquid separation is realized through vacuum filtration, and the pretreated materials are washed by ethanol, 40% (v/v) acetone solution and distilled water in sequence until the filtrate is colorless and transparent. The solid residue was dried in an oven at 105 ℃ for 24h, and the resulting sample was named Bio-DES (80 ℃).
(3) And (3) pyrolysis saccharification: a0.5 g sample of the pretreated solid was placed in a quartz tube having a diameter of 35mm and a length of 500mm, and quartz wool was inserted into both ends of the tube so that the sample was located at the center of the tube. Then selecting high-purity nitrogen as a protector, wherein the flow rate of the nitrogen is 550mL/min, when the temperature of the tube furnace is heated to 500 ℃, quickly inserting the quartz tube into the furnace for keeping for 0.5h, then taking out the quartz tube, and cooling to the room temperature. The pyrolytic bio-oil is liquefied by a condensing device and collected in a serum bottle filled with acetone. The obtained pyrolysis bio-oil was named as cornstalk pyrolysis oil (80 ℃).
Example 7
(1) Preparing an imitation eutectic solvent system: 80g of biomass light oil is put into a thick-wall pressure-resistant bottle, 40g of choline chloride is added, the mixture is placed in an oil bath kettle at the temperature of 60 ℃, and the mixture is heated and reacts for 30min at the stirring speed of 300r/min until the choline chloride is dissolved to form a uniform solution.
(2) Pretreatment of corn stalk raw materials: according to the mass ratio of 1: 20, 6g of cornstalks are poured into 120g of the pseudo-eutectic solvent system prepared in the step (1) and reacted for 5 hours at the temperature of 100 ℃ and the stirring speed of 300 r/min. After the pretreatment is finished, the solid-liquid separation is realized through vacuum filtration, and the pretreated materials are washed by ethanol, 40% (v/v) acetone solution and distilled water in sequence until the filtrate is colorless and transparent. The solid residue was dried in an oven at 105 ℃ for 24h, and the resulting sample was named Bio-DES (100 ℃).
(3) And (3) pyrolysis saccharification: 0.5g of the pretreated solid product was placed in a quartz tube having a diameter of 35mm and a length of 500mm, and quartz wool was inserted into both ends of the tube so that the sample was located at the center of the tube. Then selecting high-purity nitrogen as a protector, wherein the flow rate of the nitrogen is 550mL/min, when the temperature of the tube furnace is heated to 500 ℃, quickly inserting the quartz tube into the furnace for keeping for 0.5h, then taking out the quartz tube, and cooling to the room temperature. The pyrolytic bio-oil is liquefied by a condensing device and collected in a serum bottle filled with acetone. The obtained pyrolysis bio-oil was named as cornstalk pyrolysis oil (100 ℃).
Example 8
(1) Preparing an imitation eutectic solvent system: 80g of biomass light oil is put into a thick-wall pressure-resistant bottle, 40g of choline chloride is added, the mixture is placed in an oil bath kettle at the temperature of 60 ℃, and the mixture is heated and reacts for 30min at the stirring speed of 300r/min until the choline chloride is dissolved to form a uniform solution.
(2) Pretreatment of corn stalk raw materials: according to the mass ratio of 1: 20, 6g of cornstalks are poured into 120g of the pseudo-eutectic solvent system prepared in the step (1) and reacted for 5 hours at the temperature of 120 ℃ at the stirring speed of 300 r/min. After the pretreatment is finished, the solid-liquid separation is realized through vacuum filtration, and the pretreated materials are washed by ethanol, 40% (v/v) acetone solution and distilled water in sequence until the filtrate is colorless and transparent. The solid residue was dried in an oven at 105 ℃ for 24h, and the resulting sample was named Bio-DES (120 ℃).
(3) And (3) pyrolysis saccharification: a0.5 g sample of the pretreated solid was placed in a quartz tube having a diameter of 35mm and a length of 500mm, and quartz wool was inserted into both ends of the tube so that the sample was located at the center of the tube. Then selecting high-purity nitrogen as a protector, wherein the flow rate of the nitrogen is 550mL/min, when the temperature of the tube furnace is heated to 500 ℃, quickly inserting the quartz tube into the furnace for keeping for 0.5h, then taking out the quartz tube, and cooling to the room temperature. The pyrolytic bio-oil is liquefied by a condensing device and collected in a serum bottle filled with acetone. The obtained pyrolysis bio-oil was named as cornstalk pyrolysis oil (120 ℃).
Comparative example 1
(1) Preparing a urea eutectic solvent: 55.50g of urea is put into a thick-wall pressure-resistant bottle, 64.50g of choline chloride is added, the mixture is placed in an oil bath kettle at 60 ℃, heated and reacted for 30min at the stirring speed of 300r/min until the choline chloride is dissolved to form a uniform solution.
(2) Pretreatment of corn stalk raw materials: according to the mass ratio of 1: 20, 6g of cornstalks are poured into 120g of the urea eutectic solvent prepared in the step (1), and the mixture reacts for 5 hours at the temperature of 120 ℃ and the stirring speed of 300 r/min. After the pretreatment is finished, the solid-liquid separation is realized through vacuum filtration, and the pretreated materials are washed by ethanol, 40% (v/v) acetone solution and distilled water in sequence until the filtrate is colorless and transparent. And (3) drying the solid residue in an oven at 105 ℃ for 24h to obtain a sample named Urea-DES.
(3) And (3) pyrolysis saccharification: a0.5 g sample of the pretreated solid was placed in a quartz tube having a diameter of 35mm and a length of 500mm, and quartz wool was inserted into both ends of the tube so that the sample was located at the center of the tube. Then selecting high-purity nitrogen as a protector, wherein the flow rate of the nitrogen is 550mL/min, when the temperature of the tube furnace is heated to 500 ℃, quickly inserting the quartz tube into the furnace for keeping for 0.5h, then taking out the quartz tube, and cooling to the room temperature. The pyrolytic bio-oil is liquefied by a condensing device and collected in a serum bottle filled with acetone. The obtained pyrolysis bio-oil is named as corn stalk pyrolysis oil (Urea-DES; Urea-DES).
Comparative example 2
(1) Preparing a urea eutectic solvent: 68.89g of urea is put into a thick-wall pressure-resistant bottle, 51.11g of choline chloride is added into the bottle, the bottle is placed in an oil bath kettle at the temperature of 60 ℃, and the bottle is heated and reacts for 30min at the stirring speed of 300r/min until the choline chloride is dissolved to form a uniform solution.
(2) Pretreatment of corn stalk raw materials: according to the mass ratio of 1: 20, 6g of cornstalks are poured into 120g of the urea eutectic solvent prepared in the step (1), and the mixture reacts for 5 hours at the temperature of 120 ℃ and the stirring speed of 300 r/min. After the pretreatment is finished, the solid-liquid separation is realized through vacuum filtration, and the pretreated materials are washed by ethanol, 40% (v/v) acetone solution and distilled water in sequence until the filtrate is colorless and transparent. And (3) drying the solid residue in an oven at 105 ℃ for 24h to obtain a sample named as Phenol-DES.
(3) And (3) pyrolysis saccharification: a0.5 g sample of the pretreated solid was placed in a quartz tube having a diameter of 35mm and a length of 500mm, and quartz wool was inserted into both ends of the tube so that the sample was located at the center of the tube. Then selecting high-purity nitrogen as a protector, wherein the flow rate of the nitrogen is 550mL/min, when the temperature of the tube furnace is heated to 500 ℃, quickly inserting the quartz tube into the furnace for keeping for 0.5h, then taking out the quartz tube, and cooling to the room temperature. The pyrolytic bio-oil is liquefied by a condensing device and collected in a serum bottle filled with acetone. The obtained pyrolysis bio-oil is named as corn stalk pyrolysis oil (Phenol-DES; Phenol-DES).
Effects of the embodiment
(1) Analyzing compounds in the pyrolysis bio-oil obtained under different conditions of imitating low eutectic agent pretreatment in the embodiments 1-8 by adopting an Agilent 7890B-5977AGC/MSD gas mass spectrometer; wherein the chromatographic column is HP-5MS capillary column (30m × 0.25mm × 0.25 μm), argon is used as carrier gas, the flow rate is 77.5mL/min, and the column temperature is 40 deg.C; the column was kept at 40 ℃ for 5min and then brought to 200 ℃ at a heating rate of 10 ℃/min; finally, it was increased to 280 ℃ at a heating rate of 5 ℃/min. The ingredients in the liquid product were determined by NIST standard mass spectrometry database.
The results are shown in FIG. 4: the results show that when the proportion of the biomass light oil in the simulated eutectic solvent system is increased, the yield of the levoglucose in the pyrolysis oil is increased from 39.58mg/g to 59.87 mg/g. However, when the mass ratio of the biomass light oil to the choline chloride is from 2:1 was further increased to 4:1, which results in a significantly lower left glucose yield in the pyrolysis oil. And when the mass ratio is 2: at 1, the phenol content of the pyrolysis oil is minimized. This may be due to the lower mass ratio, which may make the pseudo-eutectic solvent system ineffective in deconstructing cornstalks. Meanwhile, the water content ratio of the excessive biomass light oil is increased, so that a hydrogen bond network in the eutectic solvent imitating system disappears, and the pretreatment effect of the eutectic solvent imitating system is weakened. The yield of levoglucose in the pyrolysis oil remained on an increasing trend as the pretreatment temperature was increased from 80 ℃ to 120 ℃. This indicates that severe pretreatment conditions are beneficial to improve the pretreatment effect of the pseudo-eutectic solvent system.
(2) The compounds in the cornstalk pyrolysis oil of example 3, comparative example 1 and comparative example 2 of the present invention were analyzed by the method of the above step (1), and the product of pyrolysis saccharification of the non-pretreated cornstalk raw material by the method of the step (3) of example 1 was used as a control.
The product distribution diagram of the cornstalk pyrolysis oil is shown in figure 5: as can be seen from the figure, the conventional low eutectic agent pretreatment also has certain influence on the quality of the bio-oil, the levoglucosan yield of Urea-DES (Urea-DES) and Phenol-DES (Phenol-DES) is respectively improved from 2.59mg/g to 23.97mg/g and 21.40mg/g, but compared with the simulated low eutectic agent pretreatment of the invention, the levoglucosan yield of the conventional low eutectic agent pretreatment sample is far lower than that of the simulated low eutectic agent pretreatment sample of the invention. This shows that the pretreatment of the eutectic-imitating agent can more effectively pretreat the original cornstalks, thereby improving the quality of the biomass pyrolysis oil and achieving higher levoglucosan yield.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for pretreating a biomass raw material to promote pyrolysis saccharification by using an imitation low cosolvent is characterized by comprising the following steps of:
(1) after mixing the biomass light oil and choline chloride, heating, stirring and dissolving to form a uniform solution, thereby obtaining an imitation eutectic solvent system;
(2) adding a biomass raw material into the simulated eutectic solvent system obtained in the step (1), stirring and reacting at 80-120 ℃, after the reaction is finished, carrying out solid-liquid separation, taking a solid, washing and drying to obtain a pretreated solid product;
(3) and (3) pyrolyzing the pretreated solid product obtained in the step (2) in a protective gas atmosphere at 450-600 ℃, and condensing and collecting the pyrolyzed volatile components to obtain the pyrolyzed bio-oil.
2. The method of claim 1 for facilitating pyrolytic saccharification by pretreatment of a biomass feedstock with a simulated low co-solvent, characterized in that:
the mass ratio of the biomass light oil to the choline chloride in the step (1) is 0.8: 1-4: 1.
3. The method of claim 2 for facilitating pyrolytic saccharification by pretreatment of a biomass feedstock with a simulated low co-solvent, characterized in that:
the mass ratio of the biomass light oil to the choline chloride in the step (1) is 2: 1-3: 1.
4. The method of claim 3 for facilitating pyrolytic saccharification by pretreatment of a biomass feedstock with a simulated low co-solvent, characterized in that:
the mass ratio of the biomass light oil to the choline chloride in the step (1) is 2: 1.
5. The method of claim 1 for facilitating pyrolytic saccharification by pretreatment of a biomass feedstock with a simulated low co-solvent, characterized in that:
the biomass raw material in the step (2) is lignocellulose and/or agricultural and forestry waste containing lignocellulose;
the mass ratio of the biomass raw material to the simulated eutectic solvent system in the step (2) is 1: 10 to 20.
6. The method of claim 5 for facilitating pyrolytic saccharification by pretreatment of a biomass feedstock with a simulated low co-solvent, characterized in that:
the biomass raw material in the step (2) is corn straw;
the particle size of the corn straw is more than 100 meshes;
the mass ratio of the biomass raw material to the simulated eutectic solvent system in the step (2) is 1: 20.
7. the method of claim 1 for facilitating pyrolytic saccharification by pretreatment of a biomass feedstock with a simulated low co-solvent, characterized in that:
the heating temperature in the step (1) is 60 +/-5 ℃;
the stirring conditions in the step (1) are as follows: stirring at 200-400 r/min for 10-60 min;
the reaction temperature in the step (2) is 100-120 ℃;
the stirring conditions in the step (2) are as follows: stirring for 5-10 h at 200-400 r/min;
the solid-liquid separation in the step (2) is realized by adopting vacuum filtration;
washing in the step (2) is to sequentially use ethanol, acetone solution and distilled water for washing;
the drying conditions in the step (2) are as follows: drying in an oven at 80-110 ℃ for 12-24 h;
the pyrolysis temperature in the step (3) is 500 ℃;
the pyrolysis time in the step (3) is 30-60 min;
the protective gas in the step (3) is nitrogen with the gas flow rate of 100-600 ml/min.
8. The method of claim 7 for facilitating pyrolytic saccharification by pretreatment of a biomass feedstock with a simulated low co-solvent, characterized in that:
the stirring conditions in the step (1) are as follows: stirring for 30min at the speed of 300 r/min;
the temperature of the reaction in the step (2) is 120 ℃;
the stirring conditions in the step (2) are as follows: stirring for 5 hours at the speed of 300 r/min;
the drying conditions in the step (2) are as follows: drying at 105 ℃ for 24 h;
the pyrolysis time in the step (3) is 30 min;
the protective gas in the step (3) is nitrogen with the gas flow rate of 550 ml/min.
9. The method for promoting pyrolysis and saccharification by utilizing the simulated low cosolvent pretreatment biomass raw material as recited in any one of claims 1 to 8, and the method is applied to agriculture and forestry waste resource recovery or preparation of pyrolysis bio-oil.
10. Use according to claim 9, characterized in that: the pyrolytic bio-oil is pyrolytic bio-oil containing more than 30mg/g of levoglucosan.
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