CN115873136A - Biomass pretreatment method and nano material - Google Patents
Biomass pretreatment method and nano material Download PDFInfo
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- CN115873136A CN115873136A CN202211583155.3A CN202211583155A CN115873136A CN 115873136 A CN115873136 A CN 115873136A CN 202211583155 A CN202211583155 A CN 202211583155A CN 115873136 A CN115873136 A CN 115873136A
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- 239000002028 Biomass Substances 0.000 title claims abstract description 61
- 238000002203 pretreatment Methods 0.000 title claims abstract description 30
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 12
- 230000005496 eutectics Effects 0.000 claims abstract description 66
- 239000002904 solvent Substances 0.000 claims abstract description 66
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229960001231 choline Drugs 0.000 claims abstract description 33
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims abstract description 33
- -1 chloride-ethylene glycol-p-methylbenzenesulfonic acid Chemical compound 0.000 claims abstract description 31
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims abstract description 18
- 235000019743 Choline chloride Nutrition 0.000 claims abstract description 18
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims abstract description 18
- 229960003178 choline chloride Drugs 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- 241000220317 Rosa Species 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- QDYGIMAMLUKRLQ-UHFFFAOYSA-N 4-methylbenzenesulfonic acid;hydrochloride Chemical compound Cl.CC1=CC=C(S(O)(=O)=O)C=C1 QDYGIMAMLUKRLQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 14
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000012467 final product Substances 0.000 description 7
- 238000004064 recycling Methods 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004108 freeze drying Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 3
- 229920001046 Nanocellulose Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 241000109329 Rosa xanthina Species 0.000 description 1
- 235000004789 Rosa xanthina Nutrition 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 239000002699 waste material Substances 0.000 description 1
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Abstract
The invention belongs to the technical field of environmental protection, and particularly relates to a biomass pretreatment method and a nano material. The biomass pretreatment method comprises the following steps: the method comprises the following steps of (1) reacting choline chloride-ethylene glycol-p-methylbenzenesulfonic acid ternary eutectic solvent with biomass; in the choline chloride-ethylene glycol-p-methylbenzenesulfonic acid ternary eutectic solvent, the molar ratio of choline chloride to ethylene glycol to p-methylbenzenesulfonic acid is 1: (0.01-1). The pretreatment method is based on a choline chloride-ethylene glycol-p-toluenesulfonic acid ternary eutectic solvent, has different solubilities on reactants and products, and well avoids side reactions generated in the reaction process; and the choline chloride-ethylene glycol-p-toluenesulfonic acid ternary eutectic solvent is easy to separate from the product, is convenient to recycle, and has a recovery rate of 90% and a purity of 90%.
Description
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a biomass pretreatment method and a nano material.
Background
With the increasing severity of environmental pollution, people have stronger environmental awareness and continuous exhaustion of fossil resources, and the development of novel renewable energy becomes a major topic with global strategic significance. Biomass is an important component of renewable energy, and is also the most promising renewable energy for industrialization and large-scale production. The reserves of biomass are extremely abundant, and it is estimated that plants on earth store approximately 10 times the annual energy consumption worldwide by photosynthesis. The development and utilization of biomass are the whole process of converting various biomass raw materials into biomass energy sources with high added values, biological materials, petroleum product substitutes, byproducts and other products through different ways. At present, the energy pressure is increasingly remarkable, and the development and utilization of biomass have important significance.
The existing pretreatment method of biomass mainly uses chemical and physical methods such as strong acid and strong alkali to destroy the structure of the biomass so as to achieve the purpose of pretreatment. However, pretreatment methods such as chemical and physical methods such as strong acid and strong alkali have problems such as serious pollution.
Therefore, an environmentally friendly method for treating biomass is required.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a method for pretreating biomass, which cuts off the structure inherent in biomass by a ternary eutectic solvent to obtain a nanoscale material. In addition, the ternary eutectic solvent in the treatment method can be recovered, the recovery rate can reach 90%, and the purity of the recovered ternary eutectic solvent can also reach 90%.
In order to achieve the purpose, the invention can adopt the following technical scheme:
in one aspect, the present invention provides a biomass pretreatment method, comprising: the method comprises the following steps of (1) reacting choline chloride-ethylene glycol-p-methylbenzenesulfonic acid ternary eutectic solvent with biomass; in the choline chloride-ethylene glycol-p-methylbenzenesulfonic acid ternary eutectic solvent, the molar ratio of choline chloride to ethylene glycol to p-methylbenzenesulfonic acid is 1: (0.01-1).
The invention also provides a nano material obtained after pretreatment by the biomass pretreatment method.
The beneficial effects of the invention include: the biomass pretreatment method provided by the invention is based on the choline chloride-ethylene glycol-p-methylbenzenesulfonic acid ternary eutectic solvent, has different solubilities on reactants and products, and well avoids side reactions generated in the reaction process; and the choline chloride-ethylene glycol-p-toluenesulfonic acid ternary eutectic solvent is easy to separate from the product, is convenient to recycle, and has a recovery rate of 90% and a purity of 90%.
Drawings
FIG. 1 is an electron micrograph of the nano lignin fragments obtained in example 2;
fig. 2 is an electron micrograph of the nanocellulose filaments obtained in example 2.
Detailed Description
The examples are given for the purpose of better illustration of the invention, but the invention is not limited to the examples. Therefore, those skilled in the art should make insubstantial modifications and adaptations to the embodiments of the present invention in light of the above teachings and remain within the scope of the invention.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. Unless the context has a significantly different meaning, the singular form of expression includes the plural form of expression. As used herein, it is understood that terms such as "comprising," "having," "including," and the like are intended to indicate the presence of features, numbers, operations, components, parts, elements, materials, or combinations thereof. The terminology of the present invention is disclosed in the specification and is not intended to exclude the possibility that one or more other features, numbers, operations, components, parts, elements, materials or combinations thereof may be present or may be added. As used herein, "/" can be interpreted as "and" or "depending on the circumstances.
The embodiment of the invention provides a biomass pretreatment method, which comprises the following steps: the method comprises the following steps of (1) reacting choline chloride-ethylene glycol-p-methylbenzenesulfonic acid ternary eutectic solvent with biomass; in the choline chloride-ethylene glycol-p-methylbenzenesulfonic acid ternary eutectic solvent, the molar ratio of choline chloride to ethylene glycol to p-methylbenzenesulfonic acid is 1: (0.01-1).
It is noted that the eutectic solvent is a mixture of two or three components formed by simply mixing a hydrogen bond acceptor and a hydrogen bond donor in a certain stoichiometric ratio under mild conditions, and is meltable at low temperature, and has great adjustability. In addition, the choline chloride-ethylene glycol-p-toluenesulfonic acid ternary eutectic solvent is wide in raw material source, low in price, low in toxicity or non-toxic.
It should be noted that the eutectic solvent can effectively remove the acting force between hydrogen bonds, cut off the inherent structure of the biomass to reach the nanometer material, and then convert the biomass into the nanometer material. In addition, in the eutectic solvent, the hydrogen bond acceptor is choline chloride and the hydrogen bond donor is ethylene glycol and p-toluenesulfonic acid. In addition, the eutectic solvent has different solubilities to reactants and products, so that side reactions generated in the reaction process are well avoided, and the yield and the purity are improved.
In some implementations, in the biomass pretreatment method, the molar ratio of choline chloride, ethylene glycol, and p-toluenesulfonic acid is 1: (0.06-0.6). In the choline chloride-ethylene glycol-p-methylbenzenesulfonic acid ternary eutectic solvent, the molar ratio of choline chloride-ethylene glycol-p-methylbenzenesulfonic acid to biomass conversion capacity is different, and the molar ratio of choline chloride, ethylene glycol, and p-methylbenzenesulfonic acid is 1: (0.01-1), the recovery rate and purity of the ternary eutectic solvent can reach 85%. Wherein, when the molar ratio is 1: (0.06-0.6), the recovery rate and purity of the ternary eutectic solvent can reach 90%, so that the molar ratio of choline chloride, ethylene glycol and p-toluenesulfonic acid is preferably 1: (0.06-0.6), such as 1. In addition, when the molar ratio of choline chloride, ethylene glycol and p-toluenesulfonic acid is less than 1:1 or more than 1: at 0.0, a ternary eutectic solvent cannot be formed.
In some implementations, in the biomass pretreatment method, the choline chloride-ethylene glycol-p-methylbenzenesulfonic acid ternary eutectic solvent is prepared by a method including: the choline chloride, the ethylene glycol and the p-toluenesulfonic acid are mixed and heated to 70-90 ℃ by a microwave reactor to react to obtain the choline chloride-p-toluenesulfonic acid.
The preparation method is characterized in that the preparation condition of the choline chloride-ethylene glycol-p-toluenesulfonate ternary eutectic solvent is mild, and the process is simple. In addition, the choline chloride-ethylene glycol-p-toluenesulfonate ternary eutectic solvent can be prepared by heating with an oil bath besides a microwave reactor, but the heating time of the oil bath is longer than that of the microwave reactor, and the recovery rate of the ternary eutectic solvent is not as high as that of the microwave reactor, so the choline chloride-ethylene glycol-p-toluenesulfonate ternary eutectic solvent is preferably prepared by heating with the microwave reactor in the invention.
In some embodiments, in the biomass pretreatment method, the reaction time of heating the microwave reactor to prepare the choline chloride-ethylene glycol-p-toluenesulfonate ternary eutectic solvent may be 10s to 120s, such as 20s, 50s or 100 s. The heating in the microwave reactor can greatly shorten the reaction time (the heating time in the oil bath is about 3 hours) compared with the heating in the oil bath.
In some implementations, in the biomass pretreatment method, the mass ratio of the biomass to the choline chloride-ethylene glycol-p-methylbenzenesulfonic acid ternary eutectic solvent is 1: (1-20). It should be noted that the mass ratio of the biomass to the choline chloride-ethylene glycol-p-toluenesulfonate ternary eutectic solvent also has an influence on the pretreatment effect, and in the invention, 1: (1-20), such as 1.
In some implementations, in the above biomass pretreatment method, the biomass is roses.
The rose is usually discarded after being used for appreciation, and the rose petals can be recycled for treatment reaction, so that the economic and social benefits are improved, and the waste is reduced.
In some implementations, in the biomass pretreatment method, the biomass is 60-mesh or less rose powder. It is to be noted that the reaction of the rose powder with the 60-mesh or smaller size and the choline chloride-ethylene glycol-p-methylbenzenesulfonic acid ternary eutectic solvent is more sufficient.
In some implementations, in the above method for pretreating biomass, the method for reacting the biomass with the choline chloride-ethylene glycol-p-toluenesulfonate ternary eutectic solvent comprises: mixing a choline chloride-ethylene glycol-p-methylbenzenesulfonic acid ternary eutectic solvent with biomass; heating to 60-120 ℃ for reaction; adding water after reaction, stirring, standing and layering; recovering supernatant, washing the lower layer with water, centrifuging, freezing, and drying to obtain nanometer material.
The operations of stirring, standing, layering, washing, centrifuging, freezing, or drying are all conventional in the art. In addition, the choline chloride-ethylene glycol-p-toluenesulfonic acid ternary eutectic solvent can be prepared by adding water, stirring, standing, layering and recovering a supernatant, namely the choline chloride-ethylene glycol-p-toluenesulfonic acid ternary eutectic solvent; the recovery is simple and convenient.
In some embodiments, in the biomass pretreatment method, the heating to 60 ℃ to 120 ℃ for reaction is performed with stirring, and the stirring speed may be 400rpm to 900rpm, such as 500rpm, 600rpm, or 800 rpm.
In some embodiments, in the biomass pretreatment method, the reaction time of the heating to 60 ℃ to 120 ℃ for reaction may be 5min to 60min, such as 10min, 30min or 50 min.
The invention also provides a nano material obtained by the pretreatment of the biomass pretreatment method. It should be noted that the biomass can be converted into the nano material by the pretreatment method in the invention, thereby expanding the utilization range of the biomass and realizing the recycling of the renewable resource ring.
For a better understanding of the present invention, the following further illustrates the contents of the present invention with reference to specific examples, but the contents of the present invention are not limited to the following examples.
1. Reaction of rose powder and eutectic solvent to prepare nano material
Example 1
Putting choline chloride, ethylene glycol and p-toluenesulfonic acid into a flask according to a molar ratio of 1; putting 10g of eutectic solvent and 1g of rose powder (60 meshes) into a beaker, adding a rotor, heating the mixture to 80 ℃ in a water bath kettle, sealing, keeping the temperature, stirring and reacting for 30min, and keeping the rotating speed at 500rpm; and adding deionized water into the obtained mixture after the reaction, stirring, standing and layering, taking out the upper layer liquid, recovering the eutectic solvent and recycling, wherein the recovery rate and the purity of the eutectic solvent are 85 percent and 81 percent respectively. And (4) putting the rest part into a centrifuge tube, adding deionized water, washing and separating, ending centrifugation until the supernatant is neutral, and putting the obtained product into a freeze dryer for freeze drying for 24 hours to obtain the final product.
Example 2
Putting choline chloride, ethylene glycol and p-toluenesulfonic acid into a flask according to a molar ratio of 1; putting 10g of eutectic solvent and 1g of rose powder (60 meshes) into a beaker, adding a rotor, heating the mixture to 80 ℃ in a water bath kettle, sealing, preserving heat, stirring and reacting for 30min, and keeping the rotating speed at 500rpm; and adding deionized water into the obtained mixture after reaction, stirring, standing and layering, taking out the upper layer liquid, recovering the eutectic solvent and recycling, wherein the recovery rate and the purity of the eutectic solvent are 94% and 91% respectively. And (4) putting the rest part into a centrifuge tube, adding deionized water, washing and separating, ending centrifugation until the supernatant is neutral, and putting the obtained product into a freeze dryer for freeze drying for 24 hours to obtain the final product.
Example 3
Choline chloride, ethylene glycol and p-toluenesulfonic acid are put into a flask according to the molar ratio of 1. Putting 10g of eutectic solvent and 1g of rose powder (60 meshes) into a beaker, adding a rotor, heating the mixture to 80 ℃ in a water bath kettle, sealing, preserving heat, stirring and reacting for 30min, and keeping the rotating speed at 500rpm; and adding deionized water into the obtained mixture after reaction, stirring, standing and layering, taking out the upper layer liquid, recovering the eutectic solvent and recycling, wherein the recovery rate and the purity of the eutectic solvent are 95% and 93% respectively. And (4) putting the rest part into a centrifuge tube, adding deionized water, washing and separating until the supernatant is neutral, finishing centrifugation, and putting the obtained product into a freeze dryer for freeze drying for 24 hours to obtain the final product.
Example 4
Putting choline chloride, ethylene glycol and p-toluenesulfonic acid into a flask according to a molar ratio of 1; putting 10g of eutectic solvent and 1g of rose powder (60 meshes) into a beaker, adding a rotor, heating the mixture to 80 ℃ in a water bath kettle, sealing, preserving heat, stirring and reacting for 30min, and keeping the rotating speed at 500rpm; and adding deionized water into the obtained mixture after the reaction, stirring, standing and layering, taking out the upper layer liquid, recovering the eutectic solvent and recycling, wherein the recovery rate and the purity of the eutectic solvent are 89% and 92% respectively. And (4) putting the rest part into a centrifuge tube, adding deionized water, washing and separating until the supernatant is neutral, finishing centrifugation, and putting the obtained product into a freeze dryer for freeze drying for 24 hours to obtain the final product.
Comparative example 1
Putting choline chloride, ethylene glycol and p-toluenesulfonic acid into a beaker according to a molar ratio of 1; putting 10g of eutectic solvent and 1g of rose powder (60 meshes) into a flask, adding a rotor, heating the mixture to 80 ℃ in a water bath kettle, sealing, keeping the temperature, stirring and reacting for 8 hours, and adding the mixture to 800rpm at the later stage when the rotation speed is 500rpm; and adding deionized water into the obtained mixture after the reaction, stirring, standing and layering, taking out the upper layer liquid, recovering the eutectic solvent and recycling, wherein the recovery rate and the purity of the eutectic solvent are 85 percent and 87 percent respectively. And (4) putting the rest part into a centrifuge tube, adding deionized water, washing and separating, ending centrifugation until the supernatant is neutral, and putting the obtained product into a freeze dryer for freeze drying for 24 hours to obtain the final product.
Comparative example 2
Putting choline chloride, ethylene glycol and p-toluenesulfonic acid into a beaker according to a molar ratio of 1; putting 10g of eutectic solvent and 1g of rose powder (60 meshes) into a flask, adding a rotor, heating the mixture to 80 ℃ in a water bath kettle, sealing, keeping the temperature, stirring and reacting for 8 hours, and adding the mixture to 800rpm at the later stage when the rotation speed is 500rpm; and adding deionized water into the obtained mixture after the reaction, stirring, standing and layering, taking out the upper layer liquid, recovering the eutectic solvent and recycling, wherein the recovery rate and the purity of the eutectic solvent are 89% and 89% respectively. And (4) putting the rest part into a centrifuge tube, adding deionized water, washing and separating until the supernatant is neutral, finishing centrifugation, and putting the obtained product into a freeze dryer for freeze drying for 24 hours to obtain the final product.
2. Characterization of prepared nanomaterials and optimization of preparation parameters
When the final products (nano lignin fragments and nano cellulose fibers) prepared in example 2 were observed by using a transmission electron microscope, the results are shown in fig. 1 and fig. 2, respectively, and the significant nanofiber structure of the final products can be seen, and the final products are relatively dense and good in shape.
In addition, through the embodiments 1 to 4, the number of the nanofibers of the final product prepared is increased along with the change of the molar ratio of the components of the eutectic solvent, which shows that the eutectic solvent of the present invention can provide hydrogen bonds well to cut off the original inherent structure of the biomass, so as to make the biomass reach a nanoscale material; however, as the molar ratio of the components of the eutectic solvent changes, the yield and purity increase and then decrease; when the molar ratio of the components of the eutectic solvent is 1.
Further, comparing comparative example 1 and comparative example 2 with example 1 and example 2, the microwave reactor used in example 1 and example 2 was heated, and the conventional oil bath used in comparative example 1 and comparative example 2 was heated, it can be seen that the heating using the microwave reactor greatly shortened the reaction time, and the recovery rate and purity of the recovered eutectic solvent were slightly higher than those of the oil bath. Therefore, the microwave reactor is preferably selected to be heated to prepare the eutectic solvent in the invention.
Finally, the above embodiments are only intended to illustrate the technical solution of the present invention and not to limit the same, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, which shall be covered by the claims of the present invention.
Claims (10)
1. A method of biomass pretreatment, comprising: the method comprises the following steps of (1) reacting choline chloride-ethylene glycol-p-methylbenzenesulfonic acid ternary eutectic solvent with biomass; in the choline chloride-ethylene glycol-p-methylbenzenesulfonic acid ternary eutectic solvent, the molar ratio of choline chloride to ethylene glycol to p-methylbenzenesulfonic acid is 1: (0.01-1).
2. The biomass pretreatment method according to claim 1, wherein a molar ratio of choline chloride, ethylene glycol, and p-toluenesulfonic acid is 1: (0.06-0.6).
3. The biomass pretreatment method according to claim 1 or 2, wherein the choline chloride-ethylene glycol-p-methylbenzenesulfonic acid ternary eutectic solvent is prepared by a method comprising: the choline chloride, the ethylene glycol and the p-toluenesulfonic acid are mixed and heated to 70-90 ℃ by a microwave reactor to react to prepare the choline chloride-p-toluenesulfonic acid.
4. The biomass pretreatment method of claim 3, wherein the reaction time is 10s to 120s.
5. The biomass pretreatment method according to claim 1, 2 or 4, wherein the mass ratio of the biomass to the choline chloride-ethylene glycol-p-methylbenzenesulfonic acid ternary eutectic solvent is 1: (1-20).
6. The method of claim 1, 2 or 4, wherein the biomass is rose.
7. The biomass pretreatment method of claim 6, wherein the biomass is 60-mesh or smaller rose powder.
8. The biomass pretreatment method according to claim 1, 2, 4, or 7, wherein the method for reacting the biomass using the choline chloride-ethylene glycol-p-methylbenzenesulfonic acid ternary eutectic solvent comprises: mixing a choline chloride-ethylene glycol-p-methylbenzenesulfonic acid ternary eutectic solvent with biomass; heating to 60-120 ℃ for reaction; adding water after reaction, stirring, standing and layering; recovering supernatant, washing the lower layer with water, centrifuging, freezing, and drying to obtain nanometer material.
9. The biomass pretreatment method according to claim 8, wherein the stirring is performed while heating to 60 ℃ to 120 ℃ for reaction, and the rotation speed of the stirring is 400rpm to 900rpm.
10. A nanomaterial obtained after pretreatment by a biomass pretreatment method according to any one of claims 1 to 9.
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